A study of the oxygen electrochemistry of ruthenium and iridium

This thesis is concerned with an investigation of the anodic behaviour of ruthenium and iridium in aqueous solution and particularly of oxygen evolution on these metals. The latter process is of major interest in the large-scale production of hydrogen gas by the electrolysis of water. The presence of low levels of ruthenium trichloride ca. 10-4 mol dm-3 in acid solution give a considerable increase in the rate of oxygen evolution from platinum and gold, but not graphite, anodes. The mechanism of this catalytic effect was investigated using potential step and a.c. impedance technique. Earlier suggestions that the effect is due to catalysis by metal ions in solution were proved to be incorrect and it was shown that ruthenium species were incorporated into the surface oxide film. Changes in the oxidation state of these ruthenium species is probably responsible for the lowering of the oxygen overvoltage. Both the theoretical and practical aspects of the reaction were complicated by the fact that at constant potential the rates of both the catalysed and the uncatalysed oxygen evolution processes exhibit an appreciable, continuous decrease with either time or degree of oxidation of the substrate. The anodic behaviour of iridium in the oxide layer region has been investigated using conventional electrochemical techniques such as cyclic voltammetry. Applying a triangular voltage sweep at 10 Hz, 0.01 to 1.50V increases the amount of electric charge which the surface can store in the oxide region. This activation effect and the mechanism of charge storage is discussed in terms of both an expanded lattice theory for oxide growth on noble metals and a more recent theory of irreversible oxide formation with subsequent stoichiometry changes. The lack of hysteresis between the anodic and cathodic peaks at ca. 0.9 V suggests that the process involved here is proton migration in a relatively thick surface layer, i.e. that the reaction involved is some type of oxide-hydroxide transition. Lack of chloride ion inhibition in the anodic region also supports the irreversible oxide formation theory; however, to account for the hydrogen region of the potential sweep a compromise theory involving partial reduction of the outer regions of iridium oxide film is proposed. The loss of charge storage capacity when the activated iridium surface is anodized for a short time above ca. 1.60 V is attributed to loss by corrosion of the outer active layer from the metal surface. The behaviour of iridium at higher anodic potentials in acid solution was investigated. Current-time curves at constant potential and Tafel plots suggested that a change in the mechanism of the oxygen evolution reaction occurs at ca. 1.8 V. Above this potential, corrosion of the metal occurred, giving rise to an absorbance in the visible spectrum of the electrolyte (λ max = 455 nm). It is suggested that the species involved was Ir(O2)2+. A similar investigation in the case of alkaline electrolyte gave no evidence for a change in mechanism at 1.8 V and corrosion of the iridium was not observed. Oxygen evolution overpotentials were much lower for iridium than for platinum in both acidic and alkaline solutions.

Water exchange rates of water-soluble manganese(III) porphyrins of therapeutical potential.

The activation parameters and the rate constants of the water-exchange reactions of Mn(III)TE-2-PyP(5+) (meso-tetrakis(N-ethylpyridinium-2-yl)porphyrin) as cationic, Mn(III)TnHex-2-PyP(5+) (meso-tetrakis(N-n-hexylpyridinium-2-yl)porphyrin) as sterically shielded cationic, and Mn(III)TSPP(3-) (meso-tetrakis(4-sulfonatophenyl)porphyrin) as anionic manganese(iii) porphyrins were determined from the temperature dependence of (17)O NMR relaxation rates. The rate constants at 298 K were obtained as 4.12 x 10(6) s(-1), 5.73 x 10(6) s(-1), and 2.74 x 10(7) s(-1), respectively. On the basis of the determined entropies of activation, an interchange-dissociative mechanism (I(d)) was proposed for the cationic complexes (DeltaS(double dagger) = approximately 0 J mol(-1) K(-1)) whereas a limiting dissociative mechanism (D) was proposed for Mn(III)TSPP(3-) complex (DeltaS(double dagger) = +79 J mol(-1) K(-1)). The obtained water exchange rate of Mn(III)TSPP(3-) corresponded well to the previously assumed value used by Koenig et al. (S. H. Koenig, R. D. Brown and M. Spiller, Magn. Reson. Med., 1987, 4, 52-260) to simulate the (1)H NMRD curves, therefore the measured value supports the theory developed for explaining the anomalous relaxivity of Mn(III)TSPP(3-) complex. A magnitude of the obtained water-exchange rate constants further confirms the suggested inner sphere electron transfer mechanism for the reactions of the two positively charged Mn(iii) porphyrins with the various biologically important oxygen and nitrogen reactive species. Due to the high biological and clinical relevance of the reactions that occur at the metal site of the studied Mn(iii) porphyrins, the determination of water exchange rates advanced our insight into their efficacy and mechanism of action, and in turn should impact their further development for both diagnostic (imaging) and therapeutic purposes.

Catalytic Water Formation on Platinum: A First-Principles Study

The study of catalytic behavior begins with one seemingly simple process, namely the hydrogenation of O to H2O on platinum. Despite the apparent simplicity its mechanism has been much debated. We have used density functional theory with,gradient corrections to examine microscopic reaction pathways for several elementary steps implicated in this fundamental catalytic process. We find that H2O formation from chemisorbed O and H atoms is a highly activated process. The largest barrier along this route, with a value of similar to1 eV, is the addition of the first H to O to produce OH. Once formed, however, OH groups are easily hydrogenated to H2O with a barrier of similar to0.2 eV. Disproportionation reactions with 1:1 and 2:1 stoichiometries of H2O and O have been examined as alternative routes for OH formation. Both stoichiometries of reaction produce OH groups with barriers that are much lower than that associated with the O + H reaction. H2O, therefore, acts as an autocatalyst in the overall H O formation process. Disproportionation with a 2:1 stoichiometry is thermodynamically and kinetically favored over disproportionation with a l:I stoichiometry. This highlights an additional (promotional) role of the second H2O molecule in this process. In support of our previous suggestion that the key intermediate in the low-temperature H2O formation reaction is a mixed OH and H2O overlayer we find that then is a very large barrier for the dissociation of the second H2O molecule in the 2:1 disproportionation process. We suggest that the proposed intermediate is then hydrogenated to H2O through a very facile proton transfer mechanism.

Measuring the solubility of benzoic acid in room temperature ionic liquids using chronoamperometric techniques

The electrochemical reduction of benzoic acid (BZA) has been studied at platinum micro-electrodes (10 and 2 mu m diameters) in acetonitrile (MeCN) and six room temperature ionic liquids (RTILs): [C(2)mim][NTf2], [C(4)min][NTf2], [C(4)mpyrr][NTf2], [C(4)mim][BF4], [C(4)mim][NO3] and [C(4)mim][PF6] (where [C(n)mim](+)=1-alkyl-3-methylimidazolium, [NTf2](-)=bis(trifluoromethylsulphonyl)imide, [C(4)mpyrr](+)=N-butyl-N-methylpyrrolidinium, [BF4](-)=tetrafluoroborate, [NO3](-)=nitrate and [PF6] = hexafluorophosphate). Based on the theoretical fitting to experimental chronoamperometric transients in [C4mpyrr][NTf2] and MeCN at several concentrations and on different size electrodes, it is suggested that a fast chemical step preceeds the electron transfer step in a CE mechanism (given below) in both RTILs and MeCN, leading to the appearance of a simple one-electron transfer mechanism.

Evaluation of cement stresses in finite element analyses of cemented orthopaedic implants

Stress analysis of the cement fixation of orthopaedic implants to bone is frequently? carried out using finite element analysis. However, the stress distribution in the cement laver is usually intricate, and it is difficult to report it in a way that facilitates comparison of implants for pre-clinical testing. To study this problem, and make recommendations for stress reporting, a finite element analysis of a hip prosthesis implanted into a synthetic composite femur is developed. Three cases are analyzed: a fully bonded implant, a debonded implant, and a debonded implant where the cement is removed distal to the stein tip. In addition to peak stresses, and contour and vector plots, a stressed volume and probability-of-failure analysis is reported. It is predicted that the peak stress is highest for the debonded stem, and that removal of the distal cement more than halves this peak stress. This would suggest that omission of the distal cement is good for polished prostheses (as practiced for the Exeter design). However; if the percentage of cement stressed above a certain threshold (say 3 MPa) is considered, then the removal of distal cement is shown to be disadvantageous because a higher volume of cement is stressed to above the threshold. Vector plots clearly demonstrate the different load transfer for bonded and debonded prostheses: A bonded stein generates maximum tensile stresses in the longitudinal direction, whereas a debonded stem generates most tensile stresses in the hoop direction, except near the tip where tensile longitudinal stresses occur due to subsidence of the stein. Removal of the cement distal to the tip allows greater subsidence but alleviates these large stresses at the tip, albeit at the expense of increased hoop stresses throughout the mantle. It is concluded that a thorough analysis of cemented implants should not report peak stress, which can be misleading, but rather stressed volume, and that vector plots should be reported if a precise analysis of the load transfer mechanism is required.

An investigation of clustered radiation-induced lesions in DNA

Recent track structure modelling studies indicate that radiation induced damage to DNA consists of a spectrum of different lesions of varying complexity. There is considerable evidence to suggest that, in repair-proficient systems, it is only the small proportion of more complex forms that is responsible for most of the biological effect. The complex lesions induced consist initially of clustered radical sites and a knowledge of their special chemistry is important in modelling how they react to form the more stable products that are processed by the repair systems. However, much of the current understanding of the chemical stage of radiation has developed from single-radical systems and there is a need to translate this to the more complex reactions that are likely to occur at the important multiple radical sites. With low LET radiation, DNA dsb may derive either from single-radical attack that damages both strands by a transfer mechanism, or from pairs of radical sites induced in close proximity, with one or more radical on each strand. With high LET radiation, modelling studies indicate that there is an increased probability of dsb arising from sites with more than two radical centres, leading to a greater frequency of more complex types of break. The spectrum of these lesions depends on the overall outcome of consecutive physical and chemical processes. The initial pattern of radical damage is determined by the energy depositions on and around the DNA, according to the type of radiation. This pattern is then modified by scavengers that inhibit the formation of radicals on the DNA, and by agents that either chemically repair (e.g. thiols) or fix (e.g. oxygen) a large fraction of these radicals. The reaction kinetics associated with clustered radical sites will differ from those of single sites: (1) because of the opportunities for interactions between the radicals themselves; and (2) because certain endpoints, e.g. a dsb, may require a combination of the products of two or more radicals. Fast response techniques using pulsed low and high LET irradiation have been established to measure the reactions of radical sites on pBR322 plasmid DNA with oxygen and thiols with a view to obtaining information about cluster size. This paper describes experimental approaches to explore the role of the chemical stage of the radiation effect in relation to lesion complexity.

Caracterização de novas membranas de titanossilicatos microporosos por ensaios de permeabilidade

O interesse crescente das membranas inorgânicas deve-se à potencial aplicação em novas áreas de investigação e da indústria, e em alternativa a operações mais convencionais. Em particular, as membranas de titanossilicatos oferecem vantagens importantes sobre as de zeólitos, pois podem ser sintetizadas sem agentes estruturantes orgânicos, para evitar a calcinação subsequente usualmente responsável por defeitos irreversíveis, exibem novas possibilidades de substituição isomórfica da matriz, permitindo um ajuste mais fino das propriedades catalíticas e de adsorção, e são capazes de separar misturas com base em diferenças de afinidade e tamanho molecular (efeito de peneiro). Os objectivos principais deste trabalho foram: i) a caracterização dinâmica de membranas do tipo zeolítico sintetizadas no Laboratório Associado CICECO, realizando-se experiências de permeação com gases puros e misturas; ii) o desenvolvimento e validação de novos modelos para a transferência de massa multicomponente através de membranas porosas pela abordagem de Maxwell-Stefan, tendo em conta os mecanismos específicos encontrados, particularmente a contribuição por difusão superficial; e iii) a modelação dos pontos experimentais medidos, bem como dados compilados da literatura. De forma a realizar os ensaios de permeação, desenhou-se, montou-se e testou-se uma instalação experimental. Para gases puros, os objectivos principais foram a medição de permeâncias a temperatura constante, por variação da pressão transmembranar r ( ΔP ), e de permeâncias a temperatura programada, conduzidas a ΔP constante. Seguidamente, calcularam-se as selectividades ideais. Em relação a misturas, a determinação de selectividades reais requer as fracções molares no permeado e no retido. Na globalidade, estudaram-se três suportes diferentes (aço inoxidável e α − alumina) e dezanove membranas de AM-3, ETS-10, ZSM-5 e zeólito 4A, utilizando-se H2, He, N2, CO2, e O2. A primeira avaliação exploratória da qualidade das membranas foi feita permeando azoto à temperatura ambiente. Assim, permeâncias superiores a 10−6 mol/m2s.Pa evidenciavam defeitos grosseiros, levando-nos a efectuar cristalizações adicionais sobre as primeiras camadas. Este procedimento foi implementado com oito membranas. Um trabalho experimental mais detalhado foi conduzido com cinco membranas. Membranas com curvas permeância-temperatura ( Π −T ) decrescentes indicam tipicamente transporte viscoso e de Knudsen, i.e. meso e macrodefeitos. Por exemplo, a membrana nº 3 de AM-3 exibiu este comportamento com H2, He, N2 e CO2 puros. A contribuição de Knudsen foi confirmada pela relação linear encontrada entre as permeâncias e o inverso da raiz quadrada da massa molar. O mecanismo viscoso foi também identificado, pois as permeâncias eram inversamente proporcionais à viscosidade do gás ou, atendendo a equações do tipo de Chapman-Enskog, directamente proporcionais a 2 0.5 k d M (onde k d é o diâmetro cinético e M a massa molar). Um comportamento de permeação distinto observou-se com a membrana nº 5 de AM-3. As permeâncias registadas a temperatura programada eram aproximadamente constantes para o N2, CO2 e O2, enquanto com o H2 cresciam significativamente. Conjuntamente elas evidenciam a ocorrência de macro, meso e microdefeitos intercristalinos. O transporte gasoso activado através dos microporos compensa o impacto diminuidor dos meso e macroporos. Ao contrário do N2, CO2 e O2, o pequeno diâmetro do hidrogénio torna-lhe possível permear através dos microporos intracristalinos, o que lhe adiciona um mecanismo de transferência responsável por esse crescimento. No que respeita à difusão superficial, o sistema CO2/ZSM-5 pode ser tomado como um exemplo paradigmático. Uma vez que este zeólito adsorve o CO2, as permeâncias diminuem com o crescimento de ΔP , em virtude de as concentrações no sólido aumentarem de forma não linear e tenderem para a saturação. Os resultados contrastantes obtidos com azoto realçam ainda mais o mecanismo superficial, pois o N2 não é adsorvido e as permeâncias medidas são constantes. Globalmente, as selectividades ideais calculadas ( α* ) variam de cerca de 1 a 4.2. Este parâmetro foi também utilizado para discriminar as melhores membranas, uma vez que baixos valores de α* denotam o escoamento viscoso não-selectivo típico de macrodefeitos. Por exemplo, o H2/CO2 na membrana nº 3 de AM-3 apresentou α* = 3.6 − 4.2 para 40–120ºC, enquanto que na membrana nº 5 de AM-3 originou α* = 2.6 − 3.1. Estes resultados corroboraram as observações anteriores, segundo as quais a membrana nº 5 era melhor do que a nº 3. Alguns ensaios foram realizados com membranas saturadas com água para aumentar a selectividade: as medições mostraram claramente uma melhoria inicial seguida de uma redução consistente de α* com o aumento da temperatura, devido à remoção das moléculas de água responsáveis pela obstrução de alguns poros. Em relação às selectividades reais de misturas contendo hidrogénio, devem ser realizadas mais experiências e a quantificação do hidrogénio deve ser melhorada. No que concerne à modelação, novos factores termodinâmicos de Maxwell- Stefan foram derivados para as isotérmicas mono e multicomponente de Nitta, Langmuir-Freundlich e Toth, tendo sido testadas com dados de equilíbrio e de permeação da literatura. (É importante realçar que só estão publicadas equações para Langmuir e Dual-Site Langmuir de componentes puros e misturas). O procedimento de validação adoptado foi exigente: i) as isotérmicas multicomponente foram previstas a partir das de gás puro; ii) os parâmetros de difusão dos componentes puros foram ajustados a dados de permeação de cada gás; iii) depois, as difusividades cruzadas de Maxwell- Stefan foram estimadas pela relação de Vignes; finalmente, v) as novas equações foram testadas usando-se estes parâmetros, tendo sido capazes de estimar com sucesso fluxos binários. Paralelamente ao enfoque principal do trabalho, derivou-se um novo modelo para permuta iónica em materiais microporosos baseado nas equações de Maxwell-Stefan. Este foi validado com dados experimentais de remoção de Hg2+ e Cd2+ de soluções aquosas usando ETS-4. A sua capacidade preditiva foi também avaliada, sendo possível concluir que se comporta muito bem. Com efeito, conseguiram-se boas previsões com parâmetros optimizados a partir de conjuntos de dados independentes. Este comportamento pode ser atribuído aos princípios físicos sólidos da teoria de Maxwell-Stefan.

Modulation of calcitonin amyloid formation by anionic lipid membranes

Tese de mestrado em Bioquímica, apresentada à Universidade de Lisboa, através da Faculdade de Ciências, 2014

The Application of the Crime against Humanity Category in Simon Ruling from Argentinean Supreme Court

En Argentine, la mise en place des lois internationales sur les droits humains dans les tribunaux locaux et son impact ne peuvent être séparés de l’histoire récente, qui a vu commettre des crimes massifs pendant la dictature de 1976 à 1983. En 1987, la Cour suprême a voté « la loi de l’Obéissance due » aussi appelée « loi de l’impunité ». Puis, en 2005, cette loi a été déclarée invalide par une nouvelle décision de la Cour suprême, car contraire à celles sur les droits humains. Les principes de la loi internationale ont prévalu pour permettre une justice efficace, ce changement soulignant le rôle de la société civile. Étant donné les réclamations grandissantes pour plus de justice dans la société argentine, le rôle de la société civile est essentiel pour comprendre la transformation et l’accroissement de la valeur normative des lois sur les droits humains dans les Cours suprêmes argentines. L’action de la société civile internationale est liée aux processus sud-américains de démocratisation, surtout dans le domaine des droits humains. La lutte contre l’impunité n’a été rendue publique que très récemment, soit seulement à partir de 2003. Elle se traduit aujourd’hui dans le rôle grandissant de l’expertise juridique et éthique dans la mise en place des politiques publiques. En fait, l’influence de la nouvelle stratégie dépend largement de la transparence des administrations bureaucratiques, des valeurs et de la volonté politique du gouvernement. Le changement légal peut être analysé selon l’acteur à l’origine du changement, le mécanisme par lequel le changement se fait et le contexte qui fournit l’opportunité pour ce changement. Dans le présent article, nous nous concentrons sur les stratégies argumentatives présentées par les juges dans la description des évènements entourant la décision de 2005. Le but de cet article est d’essayer de lier les stratégies des sociétés civiles avec l’argumentation légale dans la décision de 2005. Ces stratégies poussent à surmonter l’obstacle juridique : le fait que les crimes contre l’humanité n’étaient pas codifiés dans la loi nationale quand ils se sont déroulés (et ne le sont toujours pas.)

Photothermal deflection measurement on heat transport in GaAs epitaxial layers

In this paper, we report the in-plane and cross-plane measurements of the thermal diffusivity of double epitaxial layers of n-type GaAs doped with various concentrations of Si and a p-type Be-doped GaAs layer grown on a GaAs substrate by the molecular beam epitaxial method, using the laser-induced nondestructive photothermal deflection technique. The thermal diffusivity value is evaluated from the slope of the graph of the phase of the photothermal deflection signal as a function of pump-probe offset. Analysis of the data shows that the cross-plane thermal diffusivity is less than that of the in-plane thermal diffusivity. It is also seen that the doping concentration has a great influence on the thermal diffusivity value. Measurement of p-type Be-doped samples shows that the nature of the dopant also influences the effective thermal diffusivity value. The results are interpreted in terms of a phonon-assisted heat transfer mechanism and the various scattering process involved in the propagation of phonons.

Photothermal deflection measurement on heat transport in GaAs epitaxial layers

In this paper, we report the in-plane and cross-plane measurements of the thermal diffusivity of double epitaxial layers of n-type GaAs doped with various concentrations of Si and a p-type Be-doped GaAs layer grown on a GaAs substrate by the molecular beam epitaxial method, using the laser-induced nondestructive photothermal deflection technique. The thermal diffusivity value is evaluated from the slope of the graph of the phase of the photothermal deflection signal as a function of pump-probe offset. Analysis of the data shows that the cross-plane thermal diffusivity is less than that of the in-plane thermal diffusivity. It is also seen that the doping concentration has a great influence on the thermal diffusivity value. Measurement of p-type Be-doped samples shows that the nature of the dopant also influences the effective thermal diffusivity value. The results are interpreted in terms of a phonon-assisted heat transfer mechanism and the various scattering process involved in the propagation of phonons

Photothermal deflection measurement on heat transport in GaAs epitaxial layers

In this paper, we report the in-plane and cross-plane measurements of the thermal diffusivity of double epitaxial layers of n-type GaAs doped with various concentrations of Si and a p-type Be-doped GaAs layer grown on a GaAs substrate by the molecular beam epitaxial method, using the laser-induced nondestructive photothermal deflection technique. The thermal diffusivity value is evaluated from the slope of the graph of the phase of the photothermal deflection signal as a function of pump-probe offset. Analysis of the data shows that the cross-plane thermal diffusivity is less than that of the in-plane thermal diffusivity. It is also seen that the doping concentration has a great influence on the thermal diffusivity value. Measurement of p-type Be-doped samples shows that the nature of the dopant also influences the effective thermal diffusivity value. The results are interpreted in terms of a phonon-assisted heat transfer mechanism and the various scattering process involved in the propagation of phonons

Thermal characterization of doped polyaniline and its composites with CoPc

Thermal diffusivity of the composites of camphor sulphonic acid (CSA) doped polyaniline (PANI) and its composites with cobalt phthalocyanine (CoPc) has been measured using open cell photoacoustic technique. Analysis of the data shows that the effective thermal diffusivity value can be tuned by varying the relative volume fraction of the constituents. It is seen that polaron assisted heat transfer mechanism is dominant in CSA doped PANI and these composites exhibit a thermal diffusivity value which is intermediate to that of CSA doped PANI and CoPc. The results obtained are correlated with the electrical conductivity and hardness measurements carried out on the samples

Thermal characterization of doped polyaniline and its composites with CoPc

Thermal diffusivity of the composites of camphor sulphonic acid (CSA) doped polyaniline (PANI) and its composites with cobalt phthalocyanine (CoPc) has been measured using open cell photoacoustic technique. Analysis of the data shows that the effective thermal diffusivity value can be tuned by varying the relative volume fraction of the constituents. It is seen that polaron assisted heat transfer mechanism is dominant in CSA doped PANI and these composites exhibit a thermal diffusivity value which is intermediate to that of CSA doped PANI and CoPc. The results obtained are correlated with the electrical conductivity and hardness measurements carried out on the samples.

Thermal characterization of intrinsic and extrinsic InP using photoacoustic technique

An open photoacoustic cell operating in the low range of chopping frequency has been employed to evaluate the thermal diffusivity values of intrinsic InP and InP doped with S, Sn and Fe. The experimental set-up is calibrated by the evaluation of thermal diffusivity value of pure Si and GaAs. The present investigation shows that doped samples show a reduced value for thermal diffusivity compared to intrinsic sample. From the analysis of data it is also seen that nature of dopant clearly influences the thermal diffusivity value of semiconductors. The results are explained in terms of phonon assisted heat transfer mechanism in semiconductors