ASU Electronic Theses and Dissertations
This collection includes most of the ASU Theses and Dissertations from 2011 to present. ASU Theses and Dissertations are available in downloadable PDF format; however, a small percentage of items are under embargo. Information about the dissertations/theses includes degree information, committee members, an abstract, supporting data or media.
In addition to the electronic theses found in the ASU Digital Repository, ASU Theses and Dissertations can be found in the ASU Library Catalog.
Dissertations and Theses granted by Arizona State University are archived and made available through a joint effort of the ASU Graduate College and the ASU Libraries. For more information or questions about this collection contact or visit the Digital Repository ETD Library Guide or contact the ASU Graduate College at gradformat@asu.edu.
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Description
Metal hydride materials have been intensively studied for hydrogen storage applications. In addition to potential hydrogen economy applications, metal hydrides offer a wide variety of other interesting properties. For example, hydrogen-dominant materials, which are hydrides with the highest hydrogen content for a particular metal/semimetal composition, are predicted to display high-temperature superconductivity. On the other side of the spectrum are hydrides with small amounts of hydrogen (0.1 - 1 at.%) that are investigated as viable magnetic, thermoelectric or semiconducting materials. Research of metal hydride materials is generally important to gain fundamental understanding of metal-hydrogen interactions in materials. Hydrogenation of Zintl phases, which are defined as compounds between an active metal (alkali, alkaline earth, rare earth) and a p-block metal/semimetal, were attempted by a hot sintering method utilizing an autoclave loaded with gaseous hydrogen (< 9 MPa). Hydride formation competes with oxidative decomposition of a Zintl phase. The oxidative decomposition, which leads to a mixture of binary active metal hydride and p-block element, was observed for investigated aluminum (Al) and gallium (Ga) containing Zintl phases. However, a new phase Li2Al was discovered when Zintl phase precursors were synthesized. Using the single crystal x-ray diffraction (SCXRD), the Li2Al was found to crystallize in an orthorhombic unit cell (Cmcm) with the lattice parameters a = 4.6404(8) Å, b = 9.719(2) Å, and c = 4.4764(8) Å. Increased demand for materials with improved properties necessitates the exploration of alternative synthesis methods. Conventional metal hydride synthesis methods, like ball-milling and autoclave technique, are not responding to the demands of finding new materials. A viable alternative synthesis method is the application of high pressure for the preparation of hydrogen-dominant materials. Extreme pressures in the gigapascal ranges can open access to new metal hydrides with novel structures and properties, because of the drastically increased chemical potential of hydrogen. Pressures up to 10 GPa can be easily achieved using the multi-anvil (MA) hydrogenations while maintaining sufficient sample volume for structure and property characterization. Gigapascal MA hydrogenations using ammonia borane (BH3NH3) as an internal hydrogen source were employed in the search for new hydrogen-dominant materials. Ammonia borane has high gravimetric volume of hydrogen, and additionally the thermally activated decomposition at high pressures lead to a complete hydrogen release at reasonably low temperature. These properties make ammonia borane a desired hydrogen source material. The missing member Li2PtH6 of the series of A2PtH6 compounds (A = Na to Cs) was accessed by employing MA technique. As the known heavier analogs, the Li2PtH6 also crystallizes in a cubic K2PtCl6-type structure with a cell edge length of 6.7681(3) Å. Further gigapascal hydrogenations afforded the compounds K2SiH6 and Rb2SiH6 which are isostructural to Li2PtH6. The cubic K2SiH6 and Rb2SiH6 are built from unique hypervalent SiH62- entities with the lattice parameters of 7.8425(9) and 8.1572(4) Å, respectively. Spectroscopic analysis of hexasilicides confirmed the presence of hypervalent bonding. The Si-H stretching frequencies at 1550 cm-1 appeared considerably decreased in comparison with a normal-valent (2e2c) Si-H stretching frequencies in SiH4 at around 2200 cm-1. However, the observed stretching modes in hypervalent hexasilicides were in a reasonable agreement with Ph3SiH2- (1520 cm-1) where the hydrogen has the axial (3e4c bonded) position in the trigoal bipyramidal environment.
ContributorsPuhakainen, Kati (Author) / Häussermann, Ulrich (Thesis advisor) / Seo, Dong (Thesis advisor) / Kouvetakis, John (Committee member) / Wolf, George (Committee member) / Arizona State University (Publisher)
Created2013
Description
The connection between Hollywood costume design and the films of the 007/James Bond franchise, especially in regards to the changing perspective of the “Bond Girl”, is an intricate relationship that has previously been little researched. In the most recent Bond films, in particular, the female characters have become more powerful than the early characters and their roles within the narratives have changed with their characters taking on stronger and more integral roles. This thesis seeks to examine the films of the 007/James Bond franchise and how the rhetoric of the franchise’s costume design affects the representation of femininity and power in regards to the Bond Girls. After an overview of Bond history and costume theory, two films are analyzed as case studies: Dr. No (1962) which marks the beginning of the film franchise and Casino Royale (2006), which marks the more recent turn the films have taken. This thesis examines how the representations of Bond Girls and the use of costume design for their characters have changed over the course of the franchise from the days of Sean Connery to the recent reboot of the franchise with Daniel Craig as 007 James Bond. In addition to an examination of Bond Girl costume design, this thesis considers the role and influence of the costume designers. A designer’s vision of a character is derived from both the writing and the physical features of the actresses before them. Here this thesis considers how the rhetorical choices made by designers have contributed to an understanding of the relationship between femininity and power. Finally it shows how the costumes effect the power of the female characters and how the Bond Girls of today (Casino Royale) compare and/or contrast to Bond Girls of the past (Dr. No). This thesis combines the areas of feminist film theory and costume theory to provide an original rhetorical analysis of the Bond series in relation to costume design and examines the rhetorical statements made by the costume designers in their designs for the characters and how those statements influence the representations of the characters.
ContributorsSeverson, Andrea (Author) / Goggin, Maureen (Thesis advisor) / Ore, Ersula (Committee member) / Lamp, Kathleen (Committee member) / Arizona State University (Publisher)
Created2013
Description
In the last years of the twentieth century, while the narrative of women in other Latin American countries has received critical attention, Bolivian women's narrative has been widely ignored. The fact that the voice of Bolivian women in Latin American feminist discourse is rarely discussed in Latin American criticism is enough to justify the present study. This work focuses on three prominent Bolivian writers: Gaby Vallejos, Giovanna Rivero Santa Cruz, and Erika Bruzonic. The short stories of these three authors are characterized by accentuating certain telluric features revealed in the background of their feminine/feminist narratives. At the same time, based on the American and European feminist literary critique, this work analyzes the feminine/feminist themes mounted in the narrative of these authors. Gaby Vallejos, with a cinematic style, chronicles the life and customs of the "valluno" context, building a mosaic of different voices in dialogue. Her topics revolve around binaries: life-death, and pain and pleasure, voicing condemnation for a patriarchal society. Ericka Bruzonic deals with women and identity, memory and the breaking of lineage as an imposing structure. Her themes are built around the cosmopolitism of "paceña" urban life, and her voice transgresses the binomials established by a patriarchal society. Finally Giovanna Rivero Santa Cruz takes the life and customs of the Santa Cruz and the Guarani culture and her plots weave these elements reaching for myths and taboos, involving the reader into her stories. In this manner, her narrative makes an incursion into the conscious and unconscious realm of the readers questioning their wealth of moral and social values, their notions of heterosexuality, and sexual taboos. The three writers, with different narrative styles yet dialogical, narrate various experiences of women from different regions, social classes, ages, education, and sexual orientations. Our authors give high value to the word and the body embedded in the culture, thereby affirming their woman's voice as Bolivians and their literary presence in the context of Latin American literature.
ContributorsLopez, Norma (Author) / Urioste-Ascorra, Carmen (Thesis advisor) / Tompkins, Cynthia (Committee member) / Rosales, Jesus (Committee member) / Arizona State University (Publisher)
Created2013
Description
ABSTRACT Peptide microarrays may prove to be a powerful tool for proteomics research and clinical diagnosis applications. Fodor et al. and Maurer et al. have shown proof-of-concept methods of light- and electrochemically-directed peptide microarray fabrication on glass and semiconductor microchips respectively. In this work, peptide microarray fabrication based on the abovementioned techniques were optimized. In addition, MALDI mass spectrometry based peptide synthesis characterization on semiconductor microchips was developed and novel applications of a CombiMatrix (CBMX) platform for electrochemically controlled synthesis were explored. We have investigated performance of 2-(2-nitrophenyl)propoxycarbonyl (NPPOC) derivatives as photo-labile protecting group. Specifically, influence of substituents on 4 and 5 positions of phenyl ring of NPPOC group on the rate of photolysis and the yield of the amine was investigated. The results indicated that substituents capable of forming a π-network with the nitro group enhanced the rate of photolysis and yield. Once such properly substituted NPPOC groups were used, the rate of photolysis/yield depended on the nature of protected amino group indicating that a different chemical step during the photo-cleavage process became the rate limiting step. We also focused on electrochemically-directed parallel synthesis of high-density peptide microarrays using the CBMX technology referred to above which uses electrochemically generated acids to perform patterned chemistry. Several issues related to peptide synthesis on the CBMX platform were studied and optimized, with emphasis placed on the reactions of electro-generated acids during the deprotection step of peptide synthesis. We have developed a MALDI mass spectrometry based method to determine the chemical composition of microarray synthesis, directly on the feature. This method utilizes non-diffusional chemical cleavage from the surface, thereby making the chemical characterization of high-density microarray features simple, accurate, and amenable to high-throughput. CBMX Corp. has developed a microarray reader which is based on electro-chemical detection of redox chemical species. Several parameters of the instrument were studied and optimized and novel redox applications of peptide microarrays on CBMX platform were also investigated using the instrument. These include (i) a search of metal binding catalytic peptides to reduce overpotential associated with water oxidation reaction and (ii) an immobilization of peptide microarrays using electro-polymerized polypyrrole.
ContributorsKumar, Pallav (Author) / Woodbury, Neal (Thesis advisor) / Allen, James (Committee member) / Johnston, Stephen (Committee member) / Arizona State University (Publisher)
Created2013
Description
Las personas públicas de mujeres fuertes mexicanas generalmente se definen como desafiantes y contrarias a los roles sociales generalmente aceptados de las mujeres sumisas. Dichas personas públicas exigen atención y buscan incluirse en la cultura popular. Sin embargo, cuando se analizan mediante los rubros de la teoría queer, se revelan arquetipos heternormativos. Esta tesis examina cronológicamente la obra de tres cronistas mexicanos de los siglos XX y XXI, Salvador Novo, Carlos Monsiváis y Sara Sefchovich, analizando su retrato de mujeres fuertes que ocupan sitios urbanos públicos en la Ciudad de México. Se investigan los efectos sociales elitistas de las imágenes públicas de mujeres fuertes, revelando restricciones patriarcales de mujeres en espacios públicos y construcciones subsecuentes de personas públicas como exóticas y cosificadas, asimismo facilitando interacciones con una sociedad sumamente masculinista y machista. La falta de agencialidad social real se revela cuando el patriarcado se reafirma, a pesar de la índole disconforme de las mujeres retratadas. Los constructos de familia y de masculinidad exigen la existencia tanto del padre y del esposo ausentes como del hipermacho y de la acompañante mujer sumisa limitada a sitios privados. El retrato de mujeres fuertes en la obra analizada desnaturaliza la imagen de domesticidad, señalando que las mujeres mexicanas salen del hogar para ocupar sitios públicos en la Ciudad de México. Como la normalización del constructo de familia se cuestiona, la teoría queer se utiliza en una manera innovadora para analizar dichos retratos de mujeres fuertes y agencialidad sociopolítica.
ContributorsHolcombe, William Daniel (Author) / Foster, David William (Thesis advisor) / Tompkins, Cynthia (Committee member) / Urioste-Azcorra, Carmen (Committee member) / Arizona State University (Publisher)
Created2013
Description
Human breath is a concoction of thousands of compounds having in it a breath-print of physiological processes in the body. Though breath provides a non-invasive and easy to handle biological fluid, its analysis for clinical diagnosis is not very common. Partly the reason for this absence is unavailability of cost effective and convenient tools for such analysis. Scientific literature is full of novel sensor ideas but it is challenging to develop a working device, which are few. These challenges include trace level detection, presence of hundreds of interfering compounds, excessive humidity, different sampling regulations and personal variability. To meet these challenges as well as deliver a low cost solution, optical sensors based on specific colorimetric chemical reactions on mesoporous membranes have been developed. Sensor hardware utilizing cost effective and ubiquitously available light source (LED) and detector (webcam/photo diodes) has been developed and optimized for sensitive detection. Sample conditioning mouthpiece suitable for portable sensors is developed and integrated. The sensors are capable of communication with mobile phones realizing the idea of m-health for easy personal health monitoring in free living conditions. Nitric oxide and Acetone are chosen as analytes of interest. Nitric oxide levels in the breath correlate with lung inflammation which makes it useful for asthma management. Acetone levels increase during ketosis resulting from fat metabolism in the body. Monitoring breath acetone thus provides useful information to people with type1 diabetes, epileptic children on ketogenic diets and people following fitness plans for weight loss.
ContributorsPrabhakar, Amlendu (Author) / Tao, Nongjian (Thesis advisor) / Forzani, Erica (Committee member) / Lindsay, Stuart (Committee member) / Arizona State University (Publisher)
Created2013
Description
The ribosome is a ribozyme and central to the biosynthesis of proteins in all organisms. It has a strong bias against non-alpha-L-amino acids, such as alpha-D-amino acids and beta-amino acids. Additionally, the ribosome is only able to incorporate one amino acid in response to one codon. It has been demonstrated that reengineering of the peptidyltransferase center (PTC) of the ribosome enabled the incorporation of both alpha-D-amino acids and beta-amino acids into full length protein. Described in Chapter 2 are five modified ribosomes having modifications in the peptidyltrasnferase center in the 23S rRNA. These modified ribosomes successfully incorporated five different beta-amino acids (2.1 - 2.5) into E. coli dihydrofolate reductase (DHFR). The second project (Chapter 3) focused on the study of the modified ribosomes facilitating the incorporation of the dipeptide glycylphenylalanine (3.25) and fluorescent dipeptidomimetic 3.26 into DHFR. These ribosomes also had modifications in the peptidyltransferase center in the 23S rRNA of the 50S ribosomal subunit. The modified DHFRs having beta-amino acids 2.3 and 2.5, dipeptide glycylphenylalanine (3.25) and dipeptidomimetic 3.26 were successfully characterized by the MALDI-MS analysis of the peptide fragments produced by "in-gel" trypsin digestion of the modified proteins. The fluorescent spectra of the dipeptidomimetic 3.26 and modified DHFR having fluorescent dipeptidomimetic 3.26 were also measured. The type I and II DNA topoisomerases have been firmly established as effective molecular targets for many antitumor drugs. A "classical" topoisomerase I or II poison acts by misaligning the free hydroxyl group of the sugar moiety of DNA and preventing the reverse transesterfication reaction to religate DNA. There have been only two classes of compounds, saintopin and topopyrones, reported as dual topoisomerase I and II poisons. Chapter 4 describes the synthesis and biological evaluation of topopyrones. Compound 4.10, employed at 20 µM, was as efficient as 0.5 uM camptothecin, a potent topoisomerase I poison, in stabilizing the covalent binary complex (~30%). When compared with a known topoisomerase II poison, etoposide (at 0.5 uM), topopyorone 4.10 produced similar levels of stabilized DNA-enzyme binary complex (~34%) at 5 uM concentration.
ContributorsMaini, Rumit (Author) / Hecht, Sidney M. (Thesis advisor) / Gould, Ian (Committee member) / Yan, Hao (Committee member) / Arizona State University (Publisher)
Created2013
Description
Photosynthesis, one of the most important processes in nature, has provided an energy basis for nearly all life on Earth, as well as the fossil fuels we use today to power modern society. This research aims to mimic the photosynthetic process of converting incident solar energy into chemical potential energy in the form of a fuel via systems capable of carrying out photo-induced electron transfer to drive the production of hydrogen from water. Herein is detailed progress in using photo-induced stepwise electron transfer to drive the oxidation of water and reduction of protons to hydrogen. In the design, use of more blue absorbing porphyrin dyes to generate high-potential intermediates for oxidizing water and more red absorbing phthalocyanine dyes for forming the low potential charge needed for the production of hydrogen have been utilized. For investigating water oxidation at the photoanode, high potential porphyrins such as, bis-pyridyl porphyrins and pentafluorophenyl porphyrins have been synthesized and experiments have aimed at the co-immobilization of this dye with an IrO2-nH2O catalyst on TiO2. To drive the cathodic reaction of the water splitting photoelectrochemical cell, utilization of silicon octabutoxy-phthalocyanines have been explored, as they offer good absorption in the red to near infrared, coupled with low potential photo-excited states. Axially and peripherally substituted phthalocyanines bearing carboxylic anchoring groups for the immobilization on semiconductors such as TiO2 has been investigated. Ultimately, this work should culminate in a photoelectrochemical cell capable of splitting water to oxygen and hydrogen with the only energy input from light. A series of perylene dyes bearing multiple semi-conducting metal oxide anchoring groups have been synthesized and studied. Results have shown interfacial electron transfer between these perylenes and TiO2 nanoparticles encapsulated within reverse micelles and naked nanoparticles. The binding process was followed by monitoring the hypsochromic shift of the dye absorption spectra over time. Photoinduced electron transfer from the singlet excited state of the perylenes to the TiO2 conduction band is indicated by emission quenching of the TiO2-bound form of the dyes and confirmed by transient absorption measurements of the radical cation of the dyes and free carriers (injected electrons) in the TiO2.
ContributorsBergkamp, Jesse J (Author) / Moore, Ana L (Thesis advisor) / Mariño-Ochoa, Ernesto (Thesis advisor) / Gust, Devens J (Committee member) / Gould, Ian (Committee member) / Arizona State University (Publisher)
Created2013
Description
Developing a system capable of using solar energy to drive the conversion of an abundant and available precursor to fuel would profoundly impact humanity's energy use and thereby the condition of the global ecosystem. Such is the goal of artificial photosynthesis: to convert water to hydrogen using solar radiation as the sole energy input and ideally do so with the use of low cost, abundant materials. Constructing photoelectrochemical cells incorporating photoanodes structurally reminiscent of those used in dye sensitized photovoltaic solar cells presents one approach to establishing an artificial photosynthetic system. The work presented herein describes the production, integration, and study of water oxidation catalysts, molecular dyes, and metal oxide based photoelectrodes carried out in the pursuit of developing solar water splitting systems.
ContributorsSherman, Benjamin D (Author) / Moore, Thomas (Thesis advisor) / Moore, Ana (Committee member) / Buttry, Daniel (Committee member) / Arizona State University (Publisher)
Created2013
Description
En el siglo XXI nuestra vida se está cruzando constantemente con la tecnología, tanto que algunos declaran que nuestro mundo se ha hecho posthumano, ya que no se puede separar al ser humano de la máquina. Aunque algunos se sientan amenazados por estas tecnologías, otros están abrazando la Red Mundial, aprovechándose de las infinitas oportunidades que ofrece. Uno de estos elementos fundamentales que internet posibilita es la capacidad de comunicarse directamente con otras personas. El blog por ejemplo, o bitácora en español, permite que los usuarios se proyecten a sí mismos o a sus pseudo-identidades, sus pensamientos e ideas a través del texto que escriben en internet. También sus lectores pueden responder a estos autores inmediatamente. Los posts publicados--entradas en una página web--, aunque aparecen cronológicamente, son episodios fragmentados. Pero el blog no se limita a la producción de un texto sino que el autor puede también "jugar" con el cuerpo del texto para añadir hipervínculos y multimedia. Esta forma de escribir está cambiando lo que se considera "válido" como texto, incluso lo que se considera literatura. El objetivo de este trabajo no es estudiar la literatura digital en su totalidad, sino específicamente en algunas obras escritas por mujeres en internet. Si se considera la escritura digital como una forma de arte marginalizada, se podría decir que la escritura realizada por mujeres en internet experimenta una doble-marginalidad debido al hecho de que la literatura de mujeres siempre ha sido marginal al canon. Este estudio tomará un punto de vista transatlántico, incluyendo en el mismo a varias escritoras hispanohablantes de diferentes edades, experiencias y con variados motivos en su trabajo que publican sus obras en internet. Estas autoras incluyen las blogueras Almudena Montero (española) yMaría Amelia López Soliño (española); la periodista ciudadana Yoanis Sánchez (cubana); y la poeta digital/crítica Belén Gache (española-argentina). En esta tesis he explorado y considerado la noción de que el internet sirve como un medio de democratización puesto que, hasta cierto punto, las fronteras de género y nacionalidad desaparecen. Por esta razón, este trabajo va a considerar varias teorías tales como el postmodernismo, las teorías sobre la escritura de mujeres y teorías sobre la democratización de la tecnología para analizar la literatura que se encuentra en la red. Aunque las escritoras analizadas en este proyecto son distintas, y usan la tecnología de maneras diferentes, tienen una misma meta: expresarse libremente y comunicarse directamente con sus lectores al conectarse a internet. Mi hipótesis de trabajo consiste en que estas mujeres escriben de una manera particular--es decir, que no escriben igual a los hombres que escriben en internet--y que la red ofrece una plataforma única a las mujeres: en este espacio ellas son más activas--en oposición a la literatura tradicional-- en cuanto a compartir y publicar su propio trabajo e ideas.
ContributorsByron, Jennifer E. (Author) / Urioste-Azcorra, Carmen (Thesis advisor) / Tompkins, Cynthia (Committee member) / García-Fernández, Carlos Javier (Committee member) / Arizona State University (Publisher)
Created2013