Isoelectric trapping (IET) in multicompartment electrolyzers (MCE) has been widely used for the electrophoretic separation of ampholytic compounds such as proteins. In IET, the separation occurs in the buffering membranes that form a step-wise pH gradient in the MCE. Typically, buffering membranes have been made by copolymerizing acrylamide with Immobiline compounds, which are acidic and basic acylamido buffers. One major problem, however, is that these buffering membranes are not stable when exposed to high concentrations of acid and base due to hydrolysis of the amide bonds. Poly(vinyl alcohol)-based, or PVA-based, membranes were made as an alternative to the polyacrylamide-based membranes since they provide more hydrolytic and mechanical stability. Four mid-pH, PVA-based buffering membranes that contain single ampholytes were synthesized. These buffering membranes were used to trap small molecular weight pI markers for up to three hours, and were also used in desalting experiments to remove strong electrolytes from a solution of ampholytes. Additionally, the membranes were used in IET experiments to separate mixtures of pI markers, and to fractionate the major proteins in chicken egg white. The membranes did not show any degradation when stored in 3 M NaOH for up to 6 months and were shown to tolerate current densities as high as 16 mA/cm2. In addition, six series of PVA-based membranes, whose pH values can be tuned over the 3 < pH < 10 range, were synthesized by covalently binding aminodicarboxylic acids, and monoamines or diamines to the PVA matrix. These tunable buffering membranes were used in trapping experiments to trap ampholytes for up to three hours, and in desalting experiments to remove strong electrolytes from a solution of ampholytes. These tunable buffering membranes were also used in IET experiments to separate proteins, some with pI values that differ by only 0.1 pH unit. The tunable buffering membranes did not show any signs of degradation when exposed to 3 M NaOH for up to 3 months, and could be used in IET experiments with current densities as high as 20 mA/cm2. These tunable buffering membranes are expected to broaden the application areas of isoelectric trapping separations.

Thesis--Auburn University, 2009. / Abstract. Vita. Includes bibliographic references.

No description available.

A computer-controlled microfluidic extensional flow device is developed for trapping and manipulating micron-sized hard and soft particles. The extensional flow is generated in a diamond-shaped cross-slot that has each corner connected to a pressure-controlled liquid reservoir. By employing an imaging-based control algorithm, a particle can be made to move to an arbitrary position within the slot by adjusting the reservoir pressures and hence the fluid flow rates into/out of the slot. Thus, a soft particle can be trapped indefinitely at a point within the slot, and a known hydrodynamic force can be applied to study the dynamics of stretching and breakup of the particle. Alternatively, adhesion or coalescence dynamics of soft particles may be investigated by effecting a controlled collision between two particles. The device is validated by measuring the low interfacial tension of a compatibilized oil-water interface.

A computer-controlled microfluidic extensional flow device is developed for trapping and manipulating micron-sized hard and soft particles. The extensional flow is generated in a diamond-shaped cross-slot that has each corner connected to a pressure-controlled liquid reservoir. By employing an imaging-based control algorithm, a particle can be made to move to an arbitrary position within the slot by adjusting the reservoir pressures and hence the fluid flow rates into/out of the slot. Thus, a soft particle can be trapped indefinitely at a point within the slot, and a known hydrodynamic force can be applied to study the dynamics of stretching and breakup of the particle. Alternatively, adhesion or coalescence dynamics of soft particles may be investigated by effecting a controlled collision between two particles. The device is validated by measuring the low interfacial tension of a compatibilized oil-water interface.

This thesis presents the optical trapping of various nanometric particles (both biological and non-biological) and methods that can be used to extract information about the trapped particle from the signal transmitted through a nanoaperture trap. These methods are used to detect the excitation of vibrational modes in trapped particles due to the presence of a beat signal between two tunable trapping lasers and the molecular weight of the particle by examining the transmitted signal. Optical trapping has long been used to trap ever smaller particles in gentle non-destructive ways. In its infancy, only the optical trapping of micron sized particles was feasible. Due to various limitations, changes to the optical trapping scheme were needed to push its limits into the nanometric regime. Nanoaperture assisted optical trapping has allowed for the optical trapping of particles as small as 5 nm in diameter. By making use of specially chosen nanoapertures in gold films higher trapping strengths with lower incident laser powers have become possible. While this is an accomplishment in and of itself there are several issues associated with working with such small systems. Most notably, the ability to observe such systems is very limited. Traditional optical trapping of micron sized particles could make easy use of optical inspection, however in the nanometric regime this is not possible. It has since become a focus of the trapping community to find sophisticated ways to use the limited data available to probe these systems and their trapped targets. Once a particle is trapped the only information available about the particle is contained in the signal transmitted through the nanoaperture. The first main area of research in this thesis covers using this information to extract the molecular weight of the trapped particles for identification. In the same vein, Raman has been a tool widely used in the past to identify and probe systems of large ensembles of particles. While this is incredibly effective in some situations, it is not effective at the single particle limit. To form an analog that can be used within an optical trapping setup a new method of exciting Raman active vibrational modes with twin trapping lasers is presented. The low wavenumber vibrational spectra are presented for several different particles as well as a wide array of globular proteins. / Graduate

Chapter 1 introduces the phenomenon of oxygen toxicity and the central role played by oxygen free radicals, most notably the superoxide radical anion. The technique of spin trapping, whereby reactive free radicals are studied and identified, is then introduced. The synthesis of improved spin traps for superoxide by the preparation of 1-pyrroline 1-oxides bearing a C-3 ester or alkyl halide substituent is then discussed. Chapter 2 describes the preparation of 2-(prop-2-enyl)-aldehydes, 2-dimethoxymethylaldehydes and a 2-phenylthiomethylaldehyde. Bromination of 5,5-dimethyl-1-(prop-2-enyl)-1-pyrroline 1-oxide did not give rise to addition at the C=C double bond but recovery of the nitrone and a hydroxamic acid. Similarly, hydrohalogenation of the alkenyl-nitrone did not lead to addition at the C=C double bond. The preparation and utility of 3-(ethoxycarbonylprop-2-enyl)-5,5-dimethyl-1-pyrroline 1-oxide is then described. Chapter 3 details the preparation of 3-dimethoxymethyl-1-pyrroline 1-oxides. Acid-catalysed deprotection of these nitrone acetals did not result in the formation of the expected 3-aldehydo-5,5-dimethyl-1-pyrroline 1-oxides. Chapter 4 deals with the preparation of 5,5-dimethyl-3-phenylthiomethyl-1-pyrroline 1-oxide. Conversion of the phenylthiomethyl group to an iodomethyl group led to the loss of the nitrone. Chlorination of the nitrone gave 4-methyl-4-nitro-2-phenylthiomethylpentanoic acid. Oxidation of 5,5-dimethyl-3-ethoxycarbonyl-1-hydroxypyrrolidine resulted in the dimeric nitrone 3,3'-bis(ethoxycarbonyl)-5,5,5',5'-tetramethyl-3,3'-bi-1-pyrrolinyl 1,1-dioxide being isolated. Chapter 5 concerns the synthetic utility of α-bromoaldehydes. The preparation of 5,5-dimethyl-3-benzenesulphonyl-1-pyrroline 1-oxide is then described. Alkylation of the nitrone in the presence of sodium hydride with methylbromoacetate gave the C-3 disubstituted nitrone, 3-benzenesulphonyl-5,5-dimethyl-3-methoxycarbonylmethyl-1-pyrroline 1-oxide. Chapter 6 concerns the spin trapping reactions of the nitrones prepared in this thesis. The ESR spectra of the hydrogen atom adducts showed the magnetic non-equivalence of the β-hydrogens owing to the presence of the C-3 substituent. Spin trapping of the <I>t</I>-butoxy radical was found to be stereospecific. Apparent selectivity for the hydroxyl radical was found as no spin adducts were detected with the superoxide radical anion.

Made available in DSpace on 2014-06-11T19:32:09Z (GMT). No. of bitstreams: 0 Previous issue date: 2009-08-27Bitstream added on 2014-06-13T18:43:07Z : No. of bitstreams: 1 chanut_tgg_dr_guara.pdf: 931615 bytes, checksum: eb9339c7c510483431d4b235ce98cea8 (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Neste trabalho de tese exploramos a sugestão de Barge e Sommeria (1995) de captura de partículas em vórtices anticiclônicos que se formam devido a instabilidades na nebulosa proto-planetária. O problema dinâmico foi estudado através de simulações de um disco kepleriano bidimensional e incompressível. Examinamos o processo de concentração de partículas dentro de grandes vórtices através das equações do movimento para partículas individuais (com tamanho de 50 cm e 2,12 m) submetidas à gravidade solar e ao arrasto do gás nebular. Os vórtices levam à captura de um grande número de partículas. Mostramos que a eficácia das capturas não depende somente do valor do arrasto gasoso e da elongação do vórtice mas também do modelo do disco proto-planetário escolhido. Um achado muito importante nesse trabalho de tese pode começar a responder à questão sobre a formação planetária: colapso gravitacional ou coagulação? Quando incluímos a auto-gravidade, os resultados que obtivemos mostram que a acumulação das partículas dentro do vórtice é bem mais rápida. É um ponto muito importante na formação dos núcleos planetários até hoje bastante discutido. De fato, a formação dos núcleos planetários dos planetas gigantes precisa da acumulação de material maior que 1MÅ em muito pouco tempo para que o colapso ocorra antes do efeito gravitacional dentro do vórtice começar a expulsar os planetesimais A auto-gravidade até então bastante negligenciada por muitos autores pode ser uma ferramenta essencial a ser incluída no modelo de formação planetária para explicar tal fato. Outro resultado interessante que obtivemos foi que o crescimento por auto-sedimentação das partículas com tamanho sub-métrico, não é muito eficiente para formar planetesimais. Parece que os vórtices capturam partículas com um tamanho preferencial para formar planetesimais ou núcleos planetários. / In this thesis, we explore the suggestion of Barge & Sommeria (1995) of dust-trapping in anticyclonic vortices forming due to instabilities in the protoplanetary nebula. The dynamical problem is studied through numerical simulations of a two-dimensional incompressible Keplerian disc. We examine the process of particle concentration inside large vortex through a non-collisional N body’s code for individual particles (with sizes of 50 cm and 2,12 m) subject to the solar gravity and the nebular gas drag. The vortices tend to capture a large number of particles. We show that the effectiveness of these captures depend not only on the value of the gaseous drag and the elongation of the vortices but also on the model of the protoplanetary disc chosen. A very important finding in this thesis can start to answer the question of the planetary formation: gravitational collapse or coagulation? When we include the self-gravity, the results that we found show that the accumulation of particles inside the vortices is faster. It is a very important point in the formation of planetary embryo until today highly discussed. In fact, the formation of the giant planets embryo need the accumulation of more material than 1MÅ in a very short time such that the collapse occurs before the gravitational effect inside the vortices start to eject the planetesimals. Self-gravity, until now neglected by many authors could be an essential tool to be included in planetary formation model to explain such fact. Another interesting result that we got was that the growth for auto-sedimentation of particles with sub-metric size, is not very efficient to form planetesimal. It seems that vortices capture particles with a preferential size to form planetesimals or planetary cores.

abstract: Crystalline silicon has a relatively low absorption coefficient, and therefore, in thin silicon solar cells surface texturization plays a vital role in enhancing light absorption. Texturization is needed to increase the path length of light through the active absorbing layer. The most popular choice for surface texturization of crystalline silicon is the anisotropic wet-etching that yields pyramid-like structures. These structures have shown to be both simple to fabricate and efficient in increasing the path length; they outperform most competing surface texture. Recent studies have also shown these pyramid-like structures are not truly square-based 54.7 degree pyramids but have variable base angles and shapes. In addition, their distribution is not regular -- as is often assumed in optical models -- but random. For accurate prediction of performance of silicon solar cells, it is important to investigate the true nature of the surface texture that is achieved using anisotropic wet-etching, and its impact on light trapping. We have used atomic force microscopy (AFM) to characterize the surface topology by obtaining actual height maps that serve as input to ray tracing software. The height map also yields the base angle distribution, which is compared to the base angle distribution obtained by analyzing the angular reflectance distribution measured by spectrophotometer to validate the shape of the structures. Further validation of the measured AFM maps is done by performing pyramid density comparison with SEM micrograph of the texture. Last method employed for validation is Focused Ion Beam (FIB) that is used to mill the long section of pyramids to reveal their profile and so from that the base angle distribution is measured. After that the measured map is modified and the maps are generated keeping the positional randomness (the positions of pyramids) and height of the pyramids the same, but changing their base angles. In the end a ray tracing software is used to compare the actual measured AFM map and also the modified maps using their reflectance, transmittance, angular scattering and most importantly path length enhancement, absorbance and short circuit current with lambertian scatterer. / Dissertation/Thesis / Masters Thesis Electrical Engineering 2014

Para atingir o regime de condensação de Bose-Einstein (CBE) em gases de metais alcalinos são necessárias várias etapas: feixe desacelerado, aprisionamento magneto-óptico, aprisionamento magnético e por fim o resfriamento evaporativo. Como estamos interessados em atingir o regime de CBE precisamos nos preocupar com as várias etapas intermediárias. Neste trabalho apresentaremos a construção e caracterização de uma armadilha magnética para um gás de átomos neutros de sódio. O sistema optado por nós foi o \"folha de trevo\", com o qual conseguimos a seguinte configuração de campos magnéticos: 140 gauss de campo de fundo na direção axial, 117 gauss/cm de gradiente radial e 106 gauss/cm 2 de curvatura na direção axial. Para gerarmos esta configuração de campo e desligarmos estes campos em um tempo menor que um milisegundo foi necessária a construção de um sistema de chaveamento e controle que será descrito e caracterizado neste trabalho. Com este sistema em funcionamento observamos aproximadamente 10 8 átomos aprisionados e um tempo de 1 segundo. Além disso, observamos os átomos adaptando-se a diferentes formas de potenciais de aprisionamento / In order to obtain Bose- Einstein condensation ( BEC ) in alkali gases several steps are needed : slowing beam , magneto- optical trapping , trapping magnetic and finally evaporative cooling . Since, we are interested in achieving BEC regime we need to consider about the various intermediate steps . In this work, we present the construction and characterization of a magnetic trap for a gas neutral atom of sodium. The system we chose was the \" clover leaf \" , with which we got the following configuration of magnetic fields : 140 gauss field background in the axial direction , 117 gauss / cm radial gradient and 106 gauss / cm 2 of curvature axial direction . For generating this field configuration and disconnecting these fields in a time of less than one millisecond required the construction of a switching system and control that will be described and characterized in this work. With this system, noted in about 10 8 trapped atoms and a time of 1 second. Besides, we observe the atoms adapting to different forms of potential imprisonment