Superoxide, the product of the one-electron reduction of dioxygen, is a molecule of enormous importance. It participates in a variety of critical physiological processes and is also an important component of fuel cells where it is an intermediate in the cathodic reaction. However, the electrochemical behavior of superoxide, mainly its reduction, is not well understood. Here, the electrochemical behavior of superoxide has been investigated in acetonitrile on glassy carbon electrodes, through cyclic voltammetry experiments. By stabilizing the electrogenerated superoxide, aprotic solvents afford an opportunity to study its electrochemical reactions further. Superoxide was generated electrochemically from dioxygen at the first voltammetric peak. In the presence of hydrogen-bond donors (water, methanol, 2-propanol), the superoxide forms a complex with the donor resulting in a positive shift in the formal potential which can be analyzed to obtain formation constants for these complexes. Stronger acids (2,2,2- trifluoroethanol, 4-tert-butylphenol) result in protonation of superoxide followed by reduction to produce HO₂-. On scanning to more negative potentials a second peak is observed which is irreversible and extremely drawn out along the potential axis indicating a small value of the transfer coefficient α. Addition of hydrogenbond donors, HA, brings about a positive shift in this peak, without a noticeable change in shape. The reaction occurring at the second peak is a concerted proton-coupled electron transfer (PCET) in which the electron is transferred to superoxide and a proton is transferred from HA to superoxide forming HO₂- and A- in a concerted process. We estimate the standard potential for this reaction for the case of water as the donor. This value suggests that the reaction at the second peak occurs at very high driving forces. Kinetic simulations using both Butler-Volmer and Marcusian schemes were performed to estimate the kinetic parameters. The unusually low rate constants obtained suggest high nonadiabaticity for this PCET reaction. The reaction was also found to proceed with an unusually large reorganization energy. Consistent with a PCET, a kinetic isotope effect, HA vs. DA, was detected for the three hydrogen-bond donors.

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Submitted by Renata Lopes (renatasil82@gmail.com) on 2017-06-28T14:15:00Z No. of bitstreams: 1 rafaelfelipecoelhoneves.pdf: 2969229 bytes, checksum: cff09b57af6263220760e29c729a1382 (MD5) / Approved for entry into archive by Adriana Oliveira (adriana.oliveira@ufjf.edu.br) on 2017-08-07T21:09:40Z (GMT) No. of bitstreams: 1 rafaelfelipecoelhoneves.pdf: 2969229 bytes, checksum: cff09b57af6263220760e29c729a1382 (MD5) / Made available in DSpace on 2017-08-07T21:09:40Z (GMT). No. of bitstreams: 1 rafaelfelipecoelhoneves.pdf: 2969229 bytes, checksum: cff09b57af6263220760e29c729a1382 (MD5) Previous issue date: 2011-07-22 / CAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Em uma variedade de técnicas espectroscópicas de impacto de elétrons em amostras gasosas, é fundamental utilizar feixes de elétrons de baixas energias focalizados, colimados e monocromatizados. Sua intensidade deve ser tal que seja possível realizar a aquisição de dados em um tempo mínimo, apresentando boa estatística. O requisito da monocromatização é o que garante obter o máximo de informações espectroscópicas de dado espectro. É na região de baixas energias do elétron incidente que ocorrem importantes processos, tais como distorções na nuvem eletrônica do alvo, efeitos de polarização, efeitos de troca, captura eletrônica. Entretanto, é justamente nesta faixa de energia onde se observa maior dificuldade experimental de se trabalhar devido a alta sensibilidade do feixe eletrônico tanto incidente, como espalhado. Neste trabalho, desenvolvemos pela primeira vez no país um canhão de elétrons de baixas energias, produzindo feixes de elétrons monocromatizados. O canhão foi cuidadosamente caracterizado em termos da intensidade do feixe eletrônico incidente e sua monocromatização, atingindo-se valores de energia de 0,105 eV e intensidades de até 280 nA para feixes de 170 eV. / In a variety of spectroscopic techniques of electron impact on gaseous samples, it is essential to use electron beams of low energy focused, collimated and monochromatized. The electron beam intensity should be such that it is possible to perform data acquisition in minimal period time, with good statistics. The requirement of electron beam monochromatization ensures to get as much information of a spectrum. It is in the low-energy electron incident that important processes occur, such as distortions in the electron cloud of the target, polarization effects, exchange effects and electron capture. However, it is precisely in this energy range where the experiments are more difficult to run due to the high sensitivity of the incident and scattered electron beam. In this work, we developed first in this country an electron gun for low energies, producing monochromatized electron beams. The electron gun has been carefully characterized in terms of intensity of the incident electron beam and its capacity of monochromatization, reaching values of energy of 0.105 eV and beam intensities up to 280 nA of 170 eV.

One conventional method for studying dislocations uses the Transmission Electron Microscope (TEM), a complex and expensive piece of equipment which requires extensive specimen preparation in order to thin the specimens to electron transparent thickness. Newer High Resolution Electron Backscatter Diffraction (HREBSD) methods of determining geometrically necessary dislocation content via cross-correlation promise to be able to produce estimates of the dislocation density of the sample over a larger area with considerably less preparation time and using a much more accessible instrument. However, the accuracy of the new EBSD technique needs more experimental verification, including consideration of possible changes in the specimen dislocation density due to the different preparation methods. By comparing EBSD and TEM dislocation measurements of Electron Transparent platinum specimens prepared using the Focused Ion Beam (FIB), along with EBSD dislocations measurements of specimens prepared by both FIB and mechanical polishing techniques, this paper seeks to verify the accuracy of the new method and identify any changes in the specimens’ apparent dislocation density caused by the different preparation processes.

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Poster exhibited at GPSC Student Showcase, February 24th, 2016, University of Arizona. Recipient of the 2016 Katheryne B. Willock Library Research Award. / The nervous system is composed of two types of cells: neurons and glia. In neuronal circuits, neurons communicate through synapses and glia play a crucial modulatory role. To modulate chemical reuptake, glia send processes close to synapses and many glia directly appose or ensheathe a synapse. This structural motif is one of the elements often included in describing a vertebrate tripartite synapse, which includes a bidirectional functional neuron-glia relationship. The exact nature of this neuron-glia communication is not well understood. In the invertebrate fruit fly, we have also found that particular neurons and glia also have a bidirectional functional relationship. This allows us to ask new questions about glial morphology. Throughout multiple images, I identified particular neuronal synapses and surrounding glia. After creating a 3D reconstruction, I measured the distance between a particular neuronal synapse and its closest glial process. Interestingly, the neuronal synapses were not directly apposed or ensheathed by glia, and the distance to the closest glial process varied one-hundred-fold. With variable distance, functional communication is consistently present. These findings provide important insight into invertebrate neuron-glia communication, and offer new avenues to investigate the structural neuron-glia relationships that are required for reciprocal signaling between the two cell classes.

Studies have been carried out investigating the photochemical and photophysical properties of anthracene adsorbed on silica gel. The photochemistry and photo physics of anthracene in solution are well reported and known, hence its choice as a probe for the silica gel surface. UV -visible absorption and fluorescence spectra of anthracene adsorbed on silica gel reveal aggregate formation at very low loadings (1 % of a monolayer) indicating preferential adsorption occurs at some surface sites. Laser flash photolysis at 355 nm produces both the triplet and radical cation of anthracene, their production was found to be mono- and multi-photonic respectively. The decays of both these transients were complex and the rates increased with increasing loading. Analysis of the triplet state decay has been carried out by studying the delayed fluorescence which arises from triplet triplet annihilation. Fractal and twodimensional models have been used to describe this bimolecular decay. The coadsorption of anthracene and an electron donor having an oxidation potential below 1.09 V on silica gel causes electron transfer to occur from the electron donor to the anthracene radical cation produced following laser flash photolysis at 355 nm. Studies using a selection of electron donors with varying reduction potentials were carried out. The electron donor transfers an electron to the anthracene radical cation, thus greatly accelerating its rate of decay; for electron donors such as triphenylamine, N,N-dimethylaniline and N,N,N',N'tetramethyl- l,4-phenylenediamine the rise of the donor radical cation is observed as the anthracene cation decays. These systems were studied using fluorescence measurements and laser flash photolysis to study any fluorescence quenching and the rate of decay of both the anthracene triplet and radical cation. A selection of anthracene derivatives adsorbed onto silica gel were also briefly studied to see the effect of substituent group and its position. Symmetrically substituted dialkoxyanthracenes and 9-cyanoanthracene were used. The transient absorption spectra of the 2,3- and 2,6-dialkoxyderivatives and 9-cyanoanthracene revealed spectral similarities with that of unsubstituted anthracene. The spectra of9,10- and I,S-didecyloxyanthracene showed significant differences in the radical cation spectra to those obtained for unsubstituted anthracene.

BACKGROUND:Shewanella is a genus of facultatively anaerobic, Gram-negative bacteria that have highly adaptable metabolism which allows them to thrive in diverse environments. This quality makes them an attractive bacterial target for research in bioremediation and microbial fuel cell applications. Constraint-based modeling is a useful tool for helping researchers gain insights into the metabolic capabilities of these bacteria. However, Shewanella oneidensis MR-1 is the only strain with a genome-scale metabolic model constructed out of 21 sequenced Shewanella strains.RESULTS:In this work, we updated the model for Shewanella oneidensis MR-1 and constructed metabolic models for three other strains, namely Shewanella sp. MR-4, Shewanella sp. W3-18-1, and Shewanella denitrificans OS217 which span the genus based on the number of genes lost in comparison to MR-1. We also constructed a Shewanella core model that contains the genes shared by all 21 sequenced strains and a few non-conserved genes associated with essential reactions. Model comparisons between the five constructed models were done at two levels - for wildtype strains under different growth conditions and for knockout mutants under the same growth condition. In the first level, growth/no-growth phenotypes were predicted by the models on various carbon sources and electron acceptors. Cluster analysis of these results revealed that the MR-1 model is most similar to the W3-18-1 model, followed by the MR-4 and OS217 models when considering predicted growth phenotypes. However, a cluster analysis done based on metabolic gene content revealed that the MR-4 and W3-18-1 models are the most similar, with the MR-1 and OS217 models being more distinct from these latter two strains. As a second level of comparison, we identified differences in reaction and gene content which give rise to different functional predictions of single and double gene knockout mutants using Comparison of Networks by Gene Alignment (CONGA). Here, we showed how CONGA can be used to find biomass, metabolic, and genetic differences between models.CONCLUSIONS:We developed four strain-specific models and a general core model that can be used to do various in silico studies of Shewanella metabolism. The developed models provide a platform for a systematic investigation of Shewanella metabolism to aid researchers using Shewanella in various biotechnology applications.

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published_or_final_version / Physics / Master / Master of Philosophy