Neste trabalho reportamos a produção da primeira armadilha magneto-ótica que confina simultaneamente duas espécies atômicas distintas: Sódio e Potássio. Para podermos realizar este aprisionamento, foi necessário vencer algumas dificuldades técnicas que justificam, inclusive, a escolha dos elementos utilizados. Nossa armadilha também foi utilizada para realizar o primeiro estudo de colisões frias entre átomos de espécies diferentes. Experimentalmente, as informações sobre essas colisões são obtidas através da medida da dinâmica de perdas da armadilha de S6dio em presença e ausência de átomos frios de Potássio. Observamos que o efeito de colisões heteronucleares e dez vezes menor do que as homonucleares. Esta diferença já era esperada devido ao menor alcance dos potenciais de interação entre átomos no caso de espécies distintas. Nossos resultados são comparados a uma teoria semi-clássica simples e se encontram em bom acordo com as previsões. Introduzimos uma nova técnica que consiste em mudar repentinamente a intensidade do laser aprisionador e observar a variação do número de átomos aprisionados. Medimos a taxa de perdas por colisão entre átomos de Potássio frios como função da intensidade do laser aprisionador. Essa técnica nos permite alcançar o regime de baixas intensidades, inclusive abaixo da intensidade de saturação, sem as limitações da técnica tradicional. Aplicamos essa técnica ao aprisionamento simultâneo e medimos a taxa de perdas por colisão do sódio na presença e ausência de potássio. Com essa medida somos capazes de estimar a seção e choque entre sódio e potássio ambos no estado fundamental / In this thesis we report the production of the first magneto-optical trap that confines simultaneously two atomic species, sodium and potassium. In order to realize this experiment we had to overcome some technical difficulties that justified our choice of these two elements. This trap was used to study cold collisions between two different species. The information about these collisions is obtained experimentally from the dynamics of the sodium trap loss process in the presence and absence of potassium atoms. We observed that the heteronuclear effect is ten times smaller than the homonuclear one. This difference is explained by the smaller range of the interaction potentials between different species. Our results are compared with the theoretical predictions of the semi-classical theory and show a good agreement with the predictions. We have introduced a new technique which consists of a sudden decrease of the laser intensity, after which we observe the temporal variation in the number of trapped atoms. We have measured the loss rate coefficient between cold potassium atoms as a function of light intensity of the trapping laser. This technique allowed us to reach the very low intensity regime, as low as 30% of the saturation intensity, without compromising the loading process. We applied this technique to the simultaneous trapping and measured the loss rate coefficient between cold sodium atoms in the presence and absence of cold potassium atoms. With this measurement we can estimate the value of the cross section between sodium and potassium in the ground state

Neste trabalho resultados experimentais inéditos da taxas de perdas para o sistema Cs-K em função da intensidade do laser de aprisionamento foram obtidos. A análise dos resultados foi auxiliada pelo modelo tipo Gallagher-Pritchard que demonstrou possuir uma dependência muito forte com a velocidade de escape. Um estudo complementar ajudou na determinação dos mecanismos causadores de perdas, a catálise óptica, onde o principal resultado foi a obtenção de um resultado teórico que corresponde a observação experimental para o sistema Na-Rb, onde as perdas foram associadas a atuação do estado duplamente excitado. Compreender os mecanismos causadores de perdas pode ajudar na construção de armadilhas magneto-ópticas de grande eficiência, importantes em experimentos de medidas de propriedades atômicas. / We have investigated trap loss rate as a function of trap laser intensity for the Cs-K system. A model based on Gallagher-Pritchard type considerations, allow understand the obtained results. To correctly interpret the data, we have proposed new mechanisms, which can be proven with recent experiment in Na-Rb system.

The results presented in this dissertation have been partially presented at scientific meetings. Chapter 2 is an exact copy of the technical contents of a paper submitted to a scientific journal. The format of this paper however has been changed to comply with the format used in this dissertation. The results of this paper were partially presented at the 36th National Congress of the South African Society of Animal Science, 5 – 8 April 1998 held in Stellenbosch. In this chapter errors occurred in the execution of the trial, but these were corrected in the follow-up trial after consulting with the manufacturers. It is discussed in the paper. Results of chapter 3 were partially presented at the 5th International Sheep Veterinary Congress 21 – 25 January 2001 held in Stellenbosch and at an International Congress (The FLICS (Flystrike & Lice IPM Control Strategies) Conference, 25 – 27 June 2001, Launceston) in Tasmania by Mr. S.W.P. Cloete in 2001. The updated results are given in this chapter. The results of chapter 4 were presented at a combined congress between the Grasslands and the Animal Production Societies of South Africa (The GSSA/SASAS Joint Congress 2002. 13 – 16 May) in Christiana in 2002. The results in this chapter represent the same experimental period as was reported upon at that congress, but additional statistical analyses were executed on the same data set. Copies of the abstracts of the contributions to these meetings are attached in chapter 6. The major objective of this study initially was to evaluate the Lucitrap® system under South African conditions. During the experimental period I had an opportunity to visit Australia and meet many role players. It came under my attention that the control of the blowfly is a rather complex problem with many facets. A current issue worldwide on the use of chemicals as a control method against insects and its hazardous influence on the environment is forcing producers to minimize chemical residues in textiles and other agricultural products. An Integrated Pest Management (IPM) approach seems to be the only option. This study has been executed to try and understand some aspects of the blowfly problem for future application in such a blowfly control program.

Lipid peroxidation is well established to contribute to the etiology of many deteriorative conditions including neurodegeneration, cardiovascular disease, cancer, aging, and recently in ferroptosis—a regulated, necrotic modality of cell death that results from the accumulation of lipid hydroperoxides. Recent high-throughput screening efforts have uncovered ferrostatin-1 (Fer-1) and liproxstatin-1 (Lip-1) as two premiere inhibitors of ferroptosis. We propose that these compounds function as radical trapping antioxidants. We employ a systematic methodology of evaluating inherent radical trapping antioxidant (RTA) activity of Lip-1, Fer-1, and various aryl amine and aryl nitroxide analogues to put forward a biologically relevant mechanism of action based on our previous work in the field. Joining these observations with the efficacy of tetrahydronaphthyridinols (THNs), the results support a clear role of autoxidation in the execution of ferroptosis. Next, we expand the THN repertoire by targeting the payload towards the engine of our cells, the mitochondria. Decades of research have implicated mitochondrial dysfunction brought about by the peroxidation of mitochondrial membranes and the leaking of downstream oxidants, in the death of their symbiotic host cells. Isolated successes in the field have been demonstrated academically, though viable drugs remain to be developed, partially due to the lack of effective diagnostic tools. We endeavor to address some of these issues by investigating mitochondrially-targeted THNs (MitoTHNs) as a targeted chain-breaking antioxidant of unparalleled potency. Furthermore, we advance development of the THNs towards therapeutic applications by demonstrating their biodistribution in mice.

This dissertation explores strategies for improving photolvoltaic efficiency and reducing cost using femtosecond-laser processing methods including surface texturing and hyperdoping. Our investigations focus on two aspects: 1) texturing the silicon surface to create efficient light-trapping for thin silicon solar cells, and 2) understanding the mechanism of hyperdoping to control the doping profiles for fabricating efficient intermediate band materials. / Engineering and Applied Sciences

Thin-film photovoltaics are of great interest due to decreased manufacturing costs, improved environmental sustainability and the potential for flexible, semi-transparent, and light-weight modules. The scientific literature contains a plethora of work incorporating wavelength scale nanostructures within thin-film solar cells to increase power conversion efficiency by trapping light inside solar cell absorbing layers. One category of nanostructures, namely plasmonic nanoparticles, theoretically show great promise for their light-trapping abilities but experimental success has been limited. In this work, solar cells were designed and fabricated to incorporate multiple light-trapping mechanisms, including optical cavity resonances, waveguide mode excitation, and plasmonic effects. Due to our novel design considerations, we demonstrate a 33% increase in Jsc originating from plasmon-based enhancement mechanisms. The experimental results are complemented and confirmed by well-matching simulations which are used to further investigate the light-trapping mechanisms. The concepts demonstrated in this work can be directly translated to next-generation transition metal dichalcogenide photovoltaic devices. / Graduate / 2018-12-14

No description available.

Lipid peroxidation has been implicated in the onset and progression of many degenerative diseases, including cardiovascular disease, Alzheimer’s disease and cancer. Accordingly, for more than 50 years, considerable effort has been devoted to the design of synthetic compounds or the discovery of natural products that can slow lipid peroxidation. Despite the enormous investments made to date, no clear antioxidant strategies have emerged for the treatment and/or prevention of degenerative disease. We argue that this is because of a lack of fundamental understanding of the chemical reactivity of these compounds in relevant contexts. Herein, we describe studies of our optimized synthetic radical-trapping antioxidant (RTA) – the tetrahydronaphthyridinols (THNs). We first present the synthesis of a series of THN analogs of α-tocopherol (Nature’s premier lipid-soluble radical-trapping antioxidant) with varying sidechain substitution and then demonstrate how systematic changes in the lipophilicity of these potent antioxidants impact their peroxyl radical-trapping activities in lipid bilayers and mammalian cell culture. Their regenerability by water-soluble reductants in lipid bilayers, binding to human tocopherol transport protein (hTTP), and cytotoxicity were also evaluated to provide insight on whether this type of antioxidant can be potentially pushed toward animal studies. We also describe analogous studies of natural products such as the garlic-derived thiosulfinate allicin and the grape-derived polyphenol resveratrol. These compounds have attracted significant attention in the past 20 years due to their purported health benefits, which are often ascribed to their purported radical-trapping activities. To date, systematic studies on their radical-trapping activities in solution, lipid bilayers and mammalian cells have been lacking. We have determined that allicin and petivericin, while effective RTAs in solution, are not so in lipid bilayers. Moreover, the compounds are not antioxidants in cell culture, but instead kill the cells. Similarly, resveratrol and its dimers pallidol and quadrangularin A, are found to be inefficient RTAs in lipid bilayers. Our studies to date rather suggest that they autoxidize readily to produce hydrogen peroxide, which may induce expression of phase 2 antioxidant enzymes, affording cytoprotection. Our insights underscore the need for systematic studies of antioxidant activity in multiple contexts.

In the framework of Ph.D. thesis the evaluation of radical reactions of four groups of secondary amines R1–NH–R2 in the presence of some selected types of agents was performed using EPR spectroscopy. First group was represented by peroxoagents (3-chloroperbenzoic acid, tBuO2 radicals), the second group involved compounds of PbIV+ (PbO2, Pb(OAc)4) functioning as hydrogen-abstracting agents. In the presence of peroxyagents the formation of corresponding aminoxyl radicals R1–NO–R2 was demonstrated. In the case of surplus of tBuO2 radicals these radicals enter the consecutive reactions which products are new types of secondary aminoxyls. By the interpretation of reaction mechanism the intermediary formation of nitrones was assumed. These function in later steps of the reaction as spin traps for tBuO2 radicals. By the study of radical mechanism of amines R1–NH–R2 initiated by PbIV+ agents was proved, that these compounds hydrogen atom not only from –NH– group under formation of aminyl radicals, but also from C–H bonds in substituents R1, R2 (the formation of C-radicals). Because both groups of the radicals formed are characterized by high reactivity, their identification was possible only using spin-trapping method. In the course of the investigation of radical reactions of secondary amines the big amount of experimental EPR spectra was obtained. These exhibited in many cases very high hyperfine structure. Due to this fact it was necessary to perform the detailed evaluation on the basis of spectral simulation. Except of some special cases using this approach the interpretation of majority of registered EPR spectra was interpreted and EPR parameters were summarized in tables.

In the past decades, numerous single-molecule techniques have been developed to investigate individual bio-molecules and cellular machines. While a lot is known about the structure, localization, and interaction partners of such molecules, much less is known about their mechanical properties. To investigate the weak, non-covalent interactions that give rise to the mechanics of and between proteins, an instrument capable of resolving sub-nanometer displacements and piconewton forces is necessary. One of the most prominent biophysical tool with such capabilities is an optical tweezers. Optical tweezers is a non-invasive all-optical technique in which typically a dielectric microsphere is held by a tightly focused laser beam. This microsphere acts like a microscopic, three-dimensional spring and is used as a handle to study the biological molecule of interest. By interferometric detection methods, the resolution of optical tweezers can be in the picometer range on millisecond time scales. However, on a time scale of seconds—at which many biological reactions take place—instrumental noise such as thermal drift often limits the resolution to a few nanometers. Such a resolution is insufficient to resolve, for example, the ångstrom-level, stepwise translocation of DNA-binding enzymes corresponding to distances between single basepairs of their substrate. To reduce drift and noise, differential measurements, feedback-based drift stabilization techniques, and ‘levitated’ experiments have been developed. Such methods have the drawback of complicated and expensive experimental equipment often coupled to a reduced throughput of experiments due to a complex and serial assembly of the molecular components of the experiments. We developed a high-resolution optical tweezers apparatus capable of resolving distances on the ångstrom-level over a time range of milliseconds to 10s of seconds in surface-coupled assays. Surface-coupled assays allow for a higher throughput because the molecular components are assembled in a parallel fashion on many probes. The high resolution was a collective result of a number of simple, easy-to-implement, and cost-efficient noise reduction solutions. In particular, we reduced thermal drift by implementing a temperature feedback system with millikelvin precision—a convenient solution for biological experiments since it minimizes drift in addition to enabling the control and stabilization of the experiment’s temperature. Furthermore, we found that expanding the laser beam to a size smaller than the objective’s exit pupil optimized the amount of laser power utilized in generating the trapping forces. With lower powers, biological samples are less susceptible to photo-damage or, vice versa, with the same laser power, higher trapping forces can be achieved. With motorized and automated procedures, our instrument is optimized for high-resolution, high-throughput surface-coupled experiments probing the mechanics of individual biomolecules. In the future, the combination of this setup with single-molecule fluorescence, super-resolution microscopy or torque detection will open up new possibilities for investigating the nanomechanics of biomolecules.