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
There is a critical need for the development of clean and efficient energy sources. Hydrogen is being explored as a viable alternative to fuels in current use, many of which have limited availability and detrimental byproducts. Biological photo-production of H2 could provide a potential energy source directly manufactured from water

There is a critical need for the development of clean and efficient energy sources. Hydrogen is being explored as a viable alternative to fuels in current use, many of which have limited availability and detrimental byproducts. Biological photo-production of H2 could provide a potential energy source directly manufactured from water and sunlight. As a part of the photosynthetic electron transport chain (PETC) of the green algae Chlamydomonas reinhardtii, water is split via Photosystem II (PSII) and the electrons flow through a series of electron transfer cofactors in cytochrome b6f, plastocyanin and Photosystem I (PSI). The terminal electron acceptor of PSI is ferredoxin, from which electrons may be used to reduce NADP+ for metabolic purposes. Concomitant production of a H+ gradient allows production of energy for the cell. Under certain conditions and using the endogenous hydrogenase, excess protons and electrons from ferredoxin may be converted to molecular hydrogen. In this work it is demonstrated both that certain mutations near the quinone electron transfer cofactor in PSI can speed up electron transfer through the PETC, and also that a native [FeFe]-hydrogenase can be expressed in the C. reinhardtii chloroplast. Taken together, these research findings form the foundation for the design of a PSI-hydrogenase fusion for the direct and continuous photo-production of hydrogen in vivo.
ContributorsReifschneider, Kiera (Author) / Redding, Kevin (Thesis advisor) / Fromme, Petra (Committee member) / Jones, Anne (Committee member) / Arizona State University (Publisher)
Created2013
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Description
This study is about Thai English (ThaiE), a variety of World Englishes that is presently spoken in Thailand, as the result of the spread of English and the recent Thai government policies towards English communication in Thailand. In the study, I examined the linguistic data of spoken ThaiE, collected from

This study is about Thai English (ThaiE), a variety of World Englishes that is presently spoken in Thailand, as the result of the spread of English and the recent Thai government policies towards English communication in Thailand. In the study, I examined the linguistic data of spoken ThaiE, collected from multiple sources both in the U.S.A. and Thailand. The study made use of a qualitative approach in examining the data, which were from (i) English interviews and questionnaires with 12 highly educated Thai speakers of English during my fieldwork in the Southwestern U.S.A., Central Thailand, and Northeastern Thailand, (ii) English speech samples from the media in Thailand, i.e. television programs, a news report, and a talk radio program, and (iii) the research articles on English used by Thai speakers of English. This study describes the typology of ThaiE in terms of its morpho-syntax, phonology, and sociolinguistics, with the main focus being placed on the structural characteristics of ThaiE. Based on the data, the results show that some of the ThaiE features are similar to the World Englishes features, but some are unique to ThaiE. Therefore, I argue that ThaiE is structurally considered a new variety of World Englishes at the present time. The findings also showed an interesting result, regarding the notion of ThaiE by the fieldwork interview participants. The majority of these participants (n=6) denied the existence of ThaiE, while the minority of the participants (n=5) believed ThaiE existed, and one participant was reluctant to give the answer. The study suggested that the participants' academic backgrounds, the unfamiliar notion of ThaiE, and the level of the participants' social interaction with everyday persons may have influenced their answers to the main research question.
ContributorsRogers, Uthairat (Author) / Gelderen, Elly van (Thesis advisor) / Mailhammer, Robert (Committee member) / Adams, Karen (Committee member) / Arizona State University (Publisher)
Created2013
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Description
Despite the vast research on language carried out by the generative linguistics of Noam Chomsky and his followers since the 1950s, for theoretical reasons (mainly their attention to the mental abstraction of language structure rather than language as a performed product), historical linguistics from the start lay outside their research

Despite the vast research on language carried out by the generative linguistics of Noam Chomsky and his followers since the 1950s, for theoretical reasons (mainly their attention to the mental abstraction of language structure rather than language as a performed product), historical linguistics from the start lay outside their research interest. This study is an attempt to bridge the gap between the formalism and theoretical constructs introduced by generative grammar, whose ultimate goal is to provide not only a description but also an explanation to linguistic phenomena, and historical linguistics, which studies the evolution of language over time. This main objective is met by providing a formal account of the changes hwæðer undergoes throughout the Old English (OE) period. This seemingly inconspicuous word presents itself as a case of particular investigative interest in that it reflects the different stages proclaimed by the theoretical assumptions implemented in the study, namely the economy principles responsible for what has become known as the CP cycle: the Head Preference Principle and the Late Merge Principle, whereby pronominal hwæðer would raise to the specifier position for topicalization purposes, then after frequent use in that position, it would be base-generated there under Late Merge, until later reanalysis as the head of the Complementizer Phrase (CP) under Head Preference. Thus, I set out to classify the diverse functions of OE hwæðer by identifying and analyzing all instances as recorded in the diachronic part of the Helsinki Corpus. Both quantitative and qualitative analyses of the data have rendered the following results: 1) a fully satisfactory functional and chronological classification has been obtained by analyzing the data under investigation following a formal theoretical approach; and 2) a step-by-step historical analysis proves to be indispensable for understanding how language works at the abstract level from a historical point of view. This project is part of a growing body of research on language change which attempts to describe and explain the evolution of certain words as these change in form and function.
ContributorsParra-Guinaldo, Víctor (Author) / Gelderen, Elly van (Thesis advisor) / Bjork, Robert (Committee member) / Nilsen, Don L. F. (Committee member) / Arizona State University (Publisher)
Created2013
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Description
Linguistic subjectivity and subjectification are fields of research that are relatively new to those working in English linguistics. After a discussion of linguistic subjectivity and subjectification as they relate to English, I investigate the subjectification of a specific English adjective, and how its usage has changed over time. Subjectivity is

Linguistic subjectivity and subjectification are fields of research that are relatively new to those working in English linguistics. After a discussion of linguistic subjectivity and subjectification as they relate to English, I investigate the subjectification of a specific English adjective, and how its usage has changed over time. Subjectivity is held by many linguists of today to be the major governing factor behind the ordering of English prenominal adjectives. Through the use of a questionnaire, I investigate the effect of subjectivity on English prenominal adjective order from the perspective of the native English speaker. I then discuss the results of the questionnaire, what they mean in relation to how subjectivity affects that order, and a few of the patterns that emerged as I analyzed the data.
ContributorsSkarstedt, Luke (Author) / Gelderen, Elly van (Thesis advisor) / Bjork, Robert (Committee member) / Adams, Karen (Committee member) / Arizona State University (Publisher)
Created2013
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Description
The need for a renewable and sustainable light-driven energy source is the motivation for this work, which utilizes a challenging, yet practical and attainable bio-inspired approach to develop an artificial oxygen evolving complex, which builds upon the principles of the natural water splitting mechanism in oxygenic photosynthesis. In this work,

The need for a renewable and sustainable light-driven energy source is the motivation for this work, which utilizes a challenging, yet practical and attainable bio-inspired approach to develop an artificial oxygen evolving complex, which builds upon the principles of the natural water splitting mechanism in oxygenic photosynthesis. In this work, a stable framework consisting of a three-dimensional DNA tetrahedron has been used for the design of a bio-mimic of the Oxygen-Evolving Complex (OEC) found in natural Photosystem II (PSII). PSII is a large protein complex that evolves all the oxygen in the atmosphere, but it cannot be used directly in artificial systems, as the light reactions lead to damage of one of Photosystem II's core proteins, D1, which has to be replaced every half hour in the presence of sunlight. The final goal of the project aims to build the catalytic center of the OEC, including the Mn4CaCl metal cluster and its protein environment in the stable DNA framework of a tetrahedron, which can subsequently be connected to a photo-stable artificial reaction center that performs light-induced charge separation. Regions of the peptide sequences containing Mn4CaCl ligation sites are implemented in the design of the aOEC (artificial oxygen-evolving complex) and are attached to sites within the tetrahedron to facilitate assembly. Crystals of the tetrahedron have been obtained, and X-ray crystallography has been used for characterization. As a proof of concept, metal-binding peptides have been coupled to the DNA tetrahedron which allowed metal-containing porphyrins, specifically Fe(III) meso-Tetra(4-sulfonatophenyl) porphyrin chloride, to be encapsulated inside the DNA-tetrahedron. The porphyrins were successfully assembled inside the tetrahedron through coordination of two terminal histidines from the orthogonally oriented peptides covalently attached to the DNA. The assembly has been characterized using Electron Paramagnetic Resonance (EPR), optical spectroscopy, Dynamic Light Scattering (DLS), and x-ray crystallography. The results reveal that the spin state of the metal, iron (III), switches during assembly from the high-spin state to low-spin state.
ContributorsRendek, Kimberly Nicole (Author) / Fromme, Petra (Thesis advisor) / Chen, Julian (Committee member) / Ros, Alexandra (Committee member) / Arizona State University (Publisher)
Created2012
Description
The speech of non-native (L2) speakers of a language contains phonological rules that differentiate them from native speakers. These phonological rules characterize or distinguish accents in an L2. The Shibboleth program creates combinatorial rule-sets to describe the phonological pattern of these accents and classifies L2 speakers into their native language.

The speech of non-native (L2) speakers of a language contains phonological rules that differentiate them from native speakers. These phonological rules characterize or distinguish accents in an L2. The Shibboleth program creates combinatorial rule-sets to describe the phonological pattern of these accents and classifies L2 speakers into their native language. The training and classification is done in Shibboleth by support vector machines using a Gaussian radial basis kernel. In one experiment run using Shibboleth, the program correctly identified the native language (L1) of a speaker of unknown origin 42% of the time when there were six possible L1s in which to classify the speaker. This rate is significantly better than the 17% chance classification rate. Chi-squared test (1, N=24) =10.800, p=.0010 In a second experiment, Shibboleth was not able to determine the native language family of a speaker of unknown origin at a rate better than chance (33-44%) when the L1 was not in the transcripts used for training the language family rule-set. Chi-squared test (1, N=18) =1.000, p=.3173 The 318 participants for both experiments were from the Speech Accent Archive (Weinberger, 2013), and ranged in age from 17 to 80 years old. Forty percent of the speakers were female and 60% were male. The factor that most influenced correct classification was higher age of onset for the L2. A higher number of years spent living in an English-speaking country did not have the expected positive effect on classification.
ContributorsFrost, Wende (Author) / Gelderen, Elly van (Thesis advisor) / Perzanowski, Dennis (Committee member) / Gee, Elisabeth (Committee member) / Arizona State University (Publisher)
Created2013
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Description
Photosynthesis is the primary source of energy for most living organisms. Light harvesting complexes (LHC) play a vital role in harvesting sunlight and passing it on to the protein complexes of the electron transfer chain which create the electrochemical potential across the membrane which drives ATP synthesis. phycobilisomes (PBS) are

Photosynthesis is the primary source of energy for most living organisms. Light harvesting complexes (LHC) play a vital role in harvesting sunlight and passing it on to the protein complexes of the electron transfer chain which create the electrochemical potential across the membrane which drives ATP synthesis. phycobilisomes (PBS) are the most important LHCs in cyanobacteria. PBS is a complex of three light harvesting proteins: phycoerythrin (PE), phycocyanin (PC) and allophycocyanin (APC). This work has been done on a newly discovered cyanobacterium called Leptolyngbya Heron Island (L.HI). This study has three important goals: 1) Sequencing, assembly and annotation of the L.HI genome - Since this is a newly discovered cyanobacterium, its genome was not previously elucidated. Illumina sequencing, a type of next generation sequencing (NGS) technology was employed to sequence the genome. Unfortunately, the natural isolate contained other contaminating and potentially symbiotic bacterial populations. A novel bioinformatics strategy for separating DNA from contaminating bacterial populations from that of L.HI was devised which involves a combination of tetranucleotide frequency, %(G+C), BLAST analysis and gene annotation. 2) Structural elucidation of phycoerythrin - Phycoerythrin is the most important protein in the PBS assembly because it is one of the few light harvesting proteins which absorbs green light. The protein was crystallized and its structure solved to a resolution of 2Å. This protein contains two chemically distinct types of chromophores: phycourobilin and phycoerythrobilin. Energy transfer calculations indicate that there is unidirectional flow of energy from phycourobilin to phycoerythrobilin. Energy transfer time constants using Forster energy transfer theory have been found to be consistent with experimental data available in literature. 3) Effect of chromatic acclimation on photosystems - Chromatic acclimation is a phenomenon in which an organism modulates the ratio of PE/PC with change in light conditions. Our investigation in case of L.HI has revealed that the PE is expressed more in green light than PC in red light. This leads to unequal harvesting of light in these two states. Therefore, photosystem II expression is increased in red-light acclimatized cells coupled with an increase in number of PBS.
ContributorsPaul, Robin (Author) / Fromme, Petra (Thesis advisor) / Ros, Alexandra (Committee member) / Roberson, Robert (Committee member) / Arizona State University (Publisher)
Created2014
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Description
ABSTRACT There are many parts of speech and morphological items in a linguistic lexicon that may be optional in order to have a cohesive language with a complete range of expression. Negation is not one of them. Negation appears to be absolutely essential from a linguistic (and indeed, a psychological)

ABSTRACT There are many parts of speech and morphological items in a linguistic lexicon that may be optional in order to have a cohesive language with a complete range of expression. Negation is not one of them. Negation appears to be absolutely essential from a linguistic (and indeed, a psychological) point of view within any human language. Humans need to be able to say in some fashion "No" and to express our not doing things in various ways. During the discussions that appear in this thesis, I expound upon the historical changes that can be seen within three different language branches - North Germanic (with Gothic, Old Saxon, Old Norse, Swedish, and Icelandic), West Germanic (with English), and Celtic (with Welsh) - focusing on negation particles in particular and their position within these languages. I also examine how each of these chosen languages has seen negation shift over time in relation to Jespersen's negation cycle. Finally, I compare and contrast the results I see from these languages, demonstrating that they all three do follow a distinct negation cycle. I also explain how these three negation cycles are chronologically not in sync with one another and obviously all changed at different rates. This appears to be the case even within the different branches of the Germanic family.
ContributorsLoewenhagen, Angela C (Author) / Gelderen, Elly van (Committee member) / Bjork, Robert (Committee member) / Gillon, Carrie (Committee member) / Arizona State University (Publisher)
Created2014
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Description
Membrane proteins are a vital part of cellular structure. They are directly involved in many important cellular functions, such as uptake, signaling, respiration, and photosynthesis, among others. Despite their importance, however, less than 500 unique membrane protein structures have been determined to date. This is due to several difficulties with

Membrane proteins are a vital part of cellular structure. They are directly involved in many important cellular functions, such as uptake, signaling, respiration, and photosynthesis, among others. Despite their importance, however, less than 500 unique membrane protein structures have been determined to date. This is due to several difficulties with macromolecular crystallography, primarily the difficulty of growing large, well-ordered protein crystals. Since the first proof of concept for femtosecond nanocrystallography showing that diffraction patterns can be collected on extremely small crystals, thus negating the need to grow larger crystals, there have been many exciting advancements in the field. The technique has been proven to show high spatial resolution, thus making it a viable method for structural biology. However, due to the ultrafast nature of the technique, which allows for a lack of radiation damage in imaging, even more interesting experiments are possible, and the first temporal and spatial images of an undamaged structure could be acquired. This concept was denoted as time-resolved femtosecond nanocrystallography.

This dissertation presents on the first time-resolved data set of Photosystem II where structural changes can actually be seen without radiation damage. In order to accomplish this, new crystallization techniques had to be developed so that enough crystals could be made for the liquid jet to deliver a fully hydrated stream of crystals to the high-powered X-ray source. These changes are still in the preliminary stages due to the slightly lower resolution data obtained, but they are still a promising show of the power of this new technique. With further optimization of crystal growth methods and quality, injection technique, and continued development of data analysis software, it is only a matter of time before the ability to make movies of molecules in motion from X-ray diffraction snapshots in time exists. The work presented here is the first step in that process.
ContributorsKupitz, Christopher (Author) / Fromme, Petra (Thesis advisor) / Spence, John C. (Thesis advisor) / Redding, Kevin (Committee member) / Ros, Alexandra (Committee member) / Arizona State University (Publisher)
Created2014
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Description
Proteins and peptides fold into dynamic structures that access a broad functional landscape, however, designing artificial polypeptide systems continues to be a great chal-lenge. Conversely, deoxyribonucleic acid (DNA) engineering is now routinely used to build a wide variety of two dimensional and three dimensional (3D) nanostructures from simple hybridization based

Proteins and peptides fold into dynamic structures that access a broad functional landscape, however, designing artificial polypeptide systems continues to be a great chal-lenge. Conversely, deoxyribonucleic acid (DNA) engineering is now routinely used to build a wide variety of two dimensional and three dimensional (3D) nanostructures from simple hybridization based rules, and their functional diversity can be significantly ex-panded through site specific incorporation of the appropriate guest molecules. This dis-sertation describes a gentle methodology for using short (8 nucleotide) peptide nucleic acid (PNA) linkers to assemble polypeptides within a 3D DNA nanocage, as a proof of concept for constructing artificial catalytic centers. PNA-polypeptide conjugates were synthesized directly using microwave assisted solid phase synthesis or alternatively PNA linkers were conjugated to biologically expressed proteins using chemical crosslinking. The PNA-polypeptides hybridized to the preassembled DNA nanocage at room tempera-ture or 11 ⁰C and could be assembled in a stepwise fashion. Time resolved fluorescence anisotropy and gel electrophoresis were used to determine that a negatively charged az-urin protein was repelled outside of the negatively charged DNA nanocage, while a posi-tively charged cytochrome c protein was retained inside. Spectroelectrochemistry and an in-gel luminol oxidation assay demonstrated the cytochrome c protein remained active within the DNA nanocage and its redox potential decreased modestly by 10 mV due to the presence of the DNA nanocage. These results demonstrate the benign PNA assembly conditions are ideal for preserving polypeptide structure and function, and will facilitate the polypeptide-based assembly of artificial catalytic centers inside a stable DNA nanocage. A prospective application of assembling multiple cyclic γ-PNA-peptides to mimic the oxygen-evolving complex (OEC) catalytic active site from photosystem II (PSII) is described. In this way, the robust catalytic capacity of PSII could be utilized, without suffering the light-induced damage that occurs by the photoreactions within PSII via triplet state formation, which limits the efficiency of natural photosynthesis. There-fore, this strategy has the potential to revolutionize the process of designing and building robust catalysts by leveraging nature's recipes, and also providing a flexible and con-trolled artificial environment that might even improve them further towards commercial viability.
ContributorsFlory, Justin David (Author) / Fromme, Petra (Thesis advisor) / Yan, Hao (Committee member) / Buttry, Daniel (Committee member) / Ghirlanda, Giovanna (Committee member) / Arizona State University (Publisher)
Created2014