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
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
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
Community-based development: scaling up the correct use of misoprostol at home births in Afghanistan
Description
Globally, more than 350 000 women die annually from complications during pregnancy and childbirth (UNFPA, 2011). Nearly 99% of these, according to World Health Organization (WHO) trends (2010) occur in the developing world outside of a hospital setting with limited resources including emergency care (WHO, 2012; UNFPA, 2011). The most prevalent cause of death is postpartum hemorrhage (PPH), accounting for 25% of deaths according to WHO statistics (2012). Conditions in Afghanistan are reflective of the scope and magnitude of the problem. In Afghanistan, maternal mortality is thought to be among the highest in the world. The Afghan Mortality Survey (AMS) data implies that one Afghan woman dies about every 2 hours from pregnancy-related causes (AMS, 2010). Lack of empowerment, education and access to health care resources increase a woman's risk of dying during pregnancy (AMS, 2010). This project aims to investigate the prospects of scaling-up the correct use of misoprostol, a prostaglandin E1 analogue, to treat PPH in developing countries where skilled assistance and resources are scant. As there has been little published on the lessons learned from programs already in place, this study is experience-driven, based on the knowledge of industry experts. This study employs a concurrent triangulation approach to synthesize quantitative data obtained from previous studies with qualitative information gathered through the testimonies of key personnel who participated in pilot programs involving misoprostol. There are many obstacles to scaling-up training initiatives in Afghanistan and other low-resource areas. The analysis concludes that the most crucial factors for scaling-up community-based programs include: more studies analyzing lessons learns from community driven approaches; stronger partnerships with community health care workers; overcoming barriers like association with abortion, misuse and product issues; and a heightened global and community awareness of the severity of PPH without treatment. These results have implications for those who actively work in Afghanistan to promote maternal health and other countries that may use Afghanistan's work as a blueprint for reducing maternal mortality through community-based approaches. Keywords: Afghanistan, community-based interventions, community-driven, maternal mortality, MDG5, misoprostol, postpartum hemorrhage, reproduction, scale-up
ContributorsCristy, Candice (Author) / Grossman, Gary (Thesis advisor) / Parmentier, Mary-Jane (Committee member) / Byrd, Denise (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
This dissertation integrates humanities with social science methodologies within a critical framework, seeking to explore the relationship between the neoliberal restructuring and the intersection of gender, class and heteronormativity in contemporary China. In this project, neoliberalism is conceptualized as an art of governance centering on the intersection of race, gender, class and sexuality to create market subjects and sustain market competition. Focusing on China's recent socio-economic and cultural upheavals, this dissertation tries to address these questions: 1. How have class inequalities, binaristic gender and heteronormative discourses been employed intersectionally by the Chinese state to facilitate China's social transformation? 2. How has this process been justified and consolidated through the intersection of gender, class, sexuality and race? 3. How do the marginalized groups respond to these material and cultural practices? Building on the discursive analysis of China's televised 60th anniversary ceremony and If You Are the One, a popular Chinese reality show, as well as the data from the interview, focus group and participant observation of more than 100 informants, it is found that the intersection of gender, class and heteronormativity is central to China's neoliberal transition. A group of flexible and cheap laborers have been disarticulated and rearticulated from the population as the voluntary servitude to China's marketization and re-integration with the global economy. New controlling images, such as the bourgeois nucleus family, are created to legitimize this process. However, these disparate material and discursive practices have entailed contradictions and conflicts within the intersectional biopolitical system, and created contingent spaces of ungovernability for the marginalized groups. Building on these discursive analyses and empirical data, I reconceptualize intersectionality as a multi-dimensional-and-directional network to regulate and manage power for social organization and regulation, which grounds the biopolitical basics for the neoliberal economy. Thus I argue that we need to engage with the dynamics between the intersectional biopolitical structure and people's emerging experiences to construct a grounded utopia alternative to the neoliberal dominance for substantive social changes.
ContributorsZhang, Charlie Yi (Author) / Quan, H. L. T. (Thesis advisor) / Fonow, Mary Margaret (Thesis advisor) / Martinez, Jacqueline M. (Committee member) / Lee, Charles T. (Committee member) / Arizona State University (Publisher)
Created2013
Description
The purpose of my dissertation project is to understand how Same-Gender Loving (SGL) Black Christian men negotiate their sexuality and spirituality in spaces that are not always accepting of SGL people, by examining on how Black SGL men perform their sexual identities within hegemonic institutions that often deny their existence or outwardly seek to exclude them from their communities. I have identified three scripts that Black SGL men often follow within Black religious settings. The first script that SGL people often follow in the church is that of deliverance-- confessing their same-gender desires and maintaining that they have been delivered from those desires The second is "don't ask don't tell" performed by men who many believe and suspect of being SGL; so long as they do not publicly affirm these beliefs they are able to hold a variety of positions in their religious communities.. The last script involves accepting one's same-gender desires and also affirming one's Christian beliefs, proclaiming that the two are not at odds with one another. I examine how these scripts and/or others are performed by and on the bodies of Black SGL males in two distinct sites. The first is the career and music of former gospel star Anthony Charles Williams II (Tonex / B. Slade), who has utilized the three scripts at various times in his career. The next site is that of theatre, where I explore how these scripts have been employed in dramatic texts. By reading Christian Black SGL performance through its theological parameters, I aim to discern the avenues in which Black people in the United States are able to perform same-gender sexual identities in spaces that are constructed as "homophobic," and in so doing combat the narrative of hyper-homophobia in Black communities.
ContributorsChester, Tabitha Jamie Mary (Author) / Anderson, Lisa (Thesis advisor) / Leong, Karen J (Committee member) / Honegger, Gitta (Committee member) / Arizona State University (Publisher)
Created2013