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.
Displaying 1 - 10 of 90
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
The biological and chemical diversity of protein structure and function can be greatly expanded by position-specific incorporation of non-natural amino acids bearing a variety of functional groups. Non-cognate amino acids can be incorporated into proteins at specific sites by using orthogonal aminoacyl-tRNA synthetase/tRNA pairs in conjunction with nonsense, rare, or 4-bp codons. There has been considerable progress in developing new types of amino acids, in identifying novel methods of tRNA aminoacylation, and in expanding the genetic code to direct their position. Chemical aminoacylation of tRNAs is accomplished by acylation and ligation of a dinucleotide (pdCpA) to the 3'-terminus of truncated tRNA. This strategy allows the incorporation of a wide range of natural and unnatural amino acids into pre-determined sites, thereby facilitating the study of structure-function relationships in proteins and allowing the investigation of their biological, biochemical and biophysical properties. Described in Chapter 1 is the current methodology for synthesizing aminoacylated suppressor tRNAs. Aminoacylated suppressor tRNACUAs are typically prepared by linking pre-aminoacylated dinucleotides (aminoacyl-pdCpAs) to 74 nucleotide (nt) truncated tRNAs (tRNA-COH) via a T4 RNA ligase mediated reaction. Alternatively, there is another route outlined in Chapter 1 that utilizes a different pre-aminoacylated dinucleotide, AppA. This dinucleotide has been shown to be a suitable substrate for T4 RNA ligase mediated coupling with abbreviated tRNA-COHs for production of 76 nt aminoacyl-tRNACUAs. The synthesized suppressor tRNAs have been shown to participate in protein synthesis in vitro, in an S30 (E. coli) coupled transcription-translation system in which there is a UAG codon in the mRNA at the position corresponding to Val10. Chapter 2 describes the synthesis of two non-proteinogenic amino acids, L-thiothreonine and L-allo-thiothreonine, and their incorporation into predetermined positions of a catalytically competent dihydrofolate reductase (DHFR) analogue lacking cysteine. Here, the elaborated proteins were site-specifically derivitized with a fluorophore at the thiothreonine residue. The synthesis and incorporation of phosphorotyrosine derivatives into DHFR is illustrated in Chapter 3. Three different phosphorylated tyrosine derivatives were prepared: bis-nitrobenzylphosphoro-L-tyrosine, nitrobenzylphosphoro-L-tyrosine, and phosphoro-L-tyrosine. Their ability to participate in a protein synthesis system was also evaluated.
ContributorsNangreave, Ryan Christopher (Author) / Hecht, Sidney M. (Thesis advisor) / Yan, Hao (Committee member) / Gould, Ian (Committee member) / Arizona State University (Publisher)
Created2013
Description
Photovoltaic (PV) module nameplates typically provide the module's electrical characteristics at standard test conditions (STC). The STC conditions are: irradiance of 1000 W/m2, cell temperature of 25oC and sunlight spectrum at air mass 1.5. However, modules in the field experience a wide range of environmental conditions which affect their electrical characteristics and render the nameplate data insufficient in determining a module's overall, actual field performance. To make sound technical and financial decisions, designers and investors need additional performance data to determine the energy produced by modules operating under various field conditions. The angle of incidence (AOI) of sunlight on PV modules is one of the major parameters which dictate the amount of light reaching the solar cells. The experiment was carried out at the Arizona State University- Photovoltaic Reliability Laboratory (ASU-PRL). The data obtained was processed in accordance with the IEC 61853-2 model to obtain relative optical response of the modules (response which does not include the cosine effect). The results were then compared with theoretical models for air-glass interface and also with the empirical model developed by Sandia National Laboratories. The results showed that all modules with glass as the superstrate had identical optical response and were in agreement with both the IEC 61853-2 model and other theoretical and empirical models. The performance degradation of module over years of exposure in the field is dependent upon factors such as environmental conditions, system configuration, etc. Analyzing the degradation of power and other related performance parameters over time will provide vital information regarding possible degradation rates and mechanisms of the modules. An extensive study was conducted by previous ASU-PRL students on approximately 1700 modules which have over 13 years of hot- dry climatic field condition. An analysis of the results obtained in previous ASU-PRL studies show that the major degradation in crystalline silicon modules having glass/polymer construction is encapsulant discoloration (causing short circuit current drop) and solder bond degradation (causing fill factor drop due to series resistance increase). The power degradation for crystalline silicon modules having glass/glass construction was primarily attributed to encapsulant delamination (causing open-circuit voltage drop).
ContributorsVasantha Janakeeraman, Suryanarayana (Author) / Tamizhmani, Govindasamy (Thesis advisor) / Rogers, Bradley (Committee member) / Macia, Narciso (Committee member) / Arizona State University (Publisher)
Created2013
Description
The object of this study was a 26 year old residential Photovoltaic (PV) monocrystalline silicon (c-Si) power plant, called Solar One, built by developer John F. Long in Phoenix, Arizona (a hot-dry field condition). The task for Arizona State University Photovoltaic Reliability Laboratory (ASU-PRL) graduate students was to evaluate the power plant through visual inspection, electrical performance, and infrared thermography. The purpose of this evaluation was to measure and understand the extent of degradation to the system along with the identification of the failure modes in this hot-dry climatic condition. This 4000 module bipolar system was originally installed with a 200 kW DC output of PV array (17 degree fixed tilt) and an AC output of 175 kVA. The system was shown to degrade approximately at a rate of 2.3% per year with no apparent potential induced degradation (PID) effect. The power plant is made of two arrays, the north array and the south array. Due to a limited time frame to execute this large project, this work was performed by two masters students (Jonathan Belmont and Kolapo Olakonu) and the test results are presented in two masters theses. This thesis presents the results obtained on the north array and the other thesis presents the results obtained on the south array. The resulting study showed that PV module design, array configuration, vandalism, installation methods and Arizona environmental conditions have had an effect on this system's longevity and reliability. Ultimately, encapsulation browning, higher series resistance (potentially due to solder bond fatigue) and non-cell interconnect ribbon breakages outside the modules were determined to be the primary causes for the power loss.
ContributorsBelmont, Jonathan (Author) / Tamizhmani, Govindasamy (Thesis advisor) / Henderson, Mark (Committee member) / Rogers, Bradley (Committee member) / Arizona State University (Publisher)
Created2013
Description
Potential induced degradation (PID) due to high system voltages is one of the major degradation mechanisms in photovoltaic (PV) modules, adversely affecting their performance due to the combined effects of the following factors: system voltage, superstrate/glass surface conductivity, encapsulant conductivity, silicon nitride anti-reflection coating property and interface property (glass/encapsulant; encapsulant/cell; encapsulant/backsheet). Previous studies carried out at ASU's Photovoltaic Reliability Laboratory (ASU-PRL) showed that only negative voltage bias (positive grounded systems) adversely affects the performance of commonly available crystalline silicon modules. In previous studies, the surface conductivity of the glass surface was obtained using either conductive carbon layer extending from the glass surface to the frame or humidity inside an environmental chamber. This thesis investigates the influence of glass surface conductivity disruption on PV modules. In this study, conductive carbon was applied only on the module's glass surface without extending to the frame and the surface conductivity was disrupted (no carbon layer) at 2cm distance from the periphery of frame inner edges. This study was carried out under dry heat at two different temperatures (60 °C and 85 °C) and three different negative bias voltages (-300V, -400V, and -600V). To replicate closeness to the field conditions, half of the selected modules were pre-stressed under damp heat for 1000 hours (DH 1000) and the remaining half under 200 hours of thermal cycling (TC 200). When the surface continuity was disrupted by maintaining a 2 cm gap from the frame to the edge of the conductive layer, as demonstrated in this study, the degradation was found to be absent or negligibly small even after 35 hours of negative bias at elevated temperatures. This preliminary study appears to indicate that the modules could become immune to PID losses if the continuity of the glass surface conductivity is disrupted at the inside boundary of the frame. The surface conductivity of the glass, due to water layer formation in a humid condition, close to the frame could be disrupted just by applying a water repelling (hydrophobic) but high transmittance surface coating (such as Teflon) or modifying the frame/glass edges with water repellent properties.
ContributorsTatapudi, Sai Ravi Vasista (Author) / Tamizhmani, Govindasamy (Thesis advisor) / Srinivasan, Devarajan (Committee member) / Rogers, Bradley (Committee member) / Arizona State University (Publisher)
Created2012
Description
ABSTRACT As the use of photovoltaic (PV) modules in large power plants continues to increase globally, more studies on degradation, reliability, failure modes, and mechanisms of field aged modules are needed to predict module life expectancy based on accelerated lifetime testing of PV modules. In this work, a 26+ year old PV power plant in Phoenix, Arizona has been evaluated for performance, reliability, and durability. The PV power plant, called Solar One, is owned and operated by John F. Long's homeowners association. It is a 200 kWdc, standard test conditions (STC) rated power plant comprised of 4000 PV modules or frameless laminates, in 100 panel groups (rated at 175 kWac). The power plant is made of two center-tapped bipolar arrays, the north array and the south array. Due to a limited time frame to execute this large project, this work was performed by two masters students (Jonathan Belmont and Kolapo Olakonu) and the test results are presented in two masters theses. This thesis presents the results obtained on the south array and the other thesis presents the results obtained on the north array. Each of these two arrays is made of four sub arrays, the east sub arrays (positive and negative polarities) and the west sub arrays (positive and negative polarities), making up eight sub arrays. The evaluation and analyses of the power plant included in this thesis consists of: visual inspection, electrical performance measurements, and infrared thermography. A possible presence of potential induced degradation (PID) due to potential difference between ground and strings was also investigated. Some installation practices were also studied and found to contribute to the power loss observed in this investigation. The power output measured in 2011 for all eight sub arrays at STC is approximately 76 kWdc and represents a power loss of 62% (from 200 kW to 76 kW) over 26+ years. The 2011 measured power output for the four south sub arrays at STC is 39 kWdc and represents a power loss of 61% (from 100 kW to 39 kW) over 26+ years. Encapsulation browning and non-cell interconnect ribbon breakages were determined to be the primary causes for the power loss.
ContributorsOlakonu, Kolapo (Author) / Tamizhmani, Govindasamy (Thesis advisor) / Srinivasan, Devarajan (Committee member) / Rogers, Bradley (Committee member) / Arizona State University (Publisher)
Created2012
Description
As the genetic information storage vehicle, deoxyribonucleic acid (DNA) molecules are essential to all known living organisms and many viruses. It is amazing that such a large amount of information about how life develops can be stored in these tiny molecules. Countless scientists, especially some biologists, are trying to decipher the genetic information stored in these captivating molecules. Meanwhile, another group of researchers, nanotechnologists in particular, have discovered that the unique and concise structural features of DNA together with its information coding ability can be utilized for nano-construction efforts. This idea culminated in the birth of the field of DNA nanotechnology which is the main topic of this dissertation. The ability of rationally designed DNA strands to self-assemble into arbitrary nanostructures without external direction is the basis of this field. A series of novel design principles for DNA nanotechnology are presented here, from topological DNA nanostructures to complex and curved DNA nanostructures, from pure DNA nanostructures to hybrid RNA/DNA nanostructures. As one of the most important and pioneering fields in controlling the assembly of materials (both DNA and other materials) at the nanoscale, DNA nanotechnology is developing at a dramatic speed and as more and more construction approaches are invented, exciting advances will emerge in ways that we may or may not predict.
ContributorsHan, Dongran (Author) / Yan, Hao (Thesis advisor) / Liu, Yan (Thesis advisor) / Ros, Anexandra (Committee member) / Gould, Ian (Committee member) / Arizona State University (Publisher)
Created2012
Description
While the piezoelectric effect has been around for some time, it has only recently caught interest as a potential sustainable energy harvesting device. Piezoelectric energy harvesting has been developed for shoes and panels, but has yet to be integrated into a marketable bicycle tire. For this thesis, the development and feasibility of a piezoelectric tire was done. This includes the development of a circuit that incorporates piezoceramic elements, energy harvesting circuitry, and an energy storage device. A single phase circuit was designed using an ac-dc diode rectifier. An electrolytic capacitor was used as the energy storage device. A financial feasibility was also done to determine targets for manufacturing cost and sales price. These models take into account market trends for high performance tires, economies of scale, and the possibility of government subsidies. This research will help understand the potential for the marketability of a piezoelectric energy harvesting tire that can create electricity for remote use. This study found that there are many obstacles that must be addressed before a piezoelectric tire can be marketed to the general public. The power output of this device is miniscule compared to an alkaline battery. In order for this device to approach the power output of an alkaline battery the weight of the device would also become an issue. Additionally this device is very costly compared to the average bicycle tire. Lastly, this device is extreme fragile and easily broken. In order for this device to become marketable the issues of power output, cost, weight, and durability must all be successfully overcome.
ContributorsMalotte, Christopher (Author) / Madakannan, Arunachalanadar (Thesis advisor) / Srinivasan, Devarajan (Committee member) / Rogers, Bradley (Committee member) / Arizona State University (Publisher)
Created2012
Description
A clean and sustainable alternative to fossil fuels is solar energy. For efficient use of solar energy to be realized, artificial systems that can effectively capture and convert sunlight into a usable form of energy have to be developed. In natural photosynthesis, antenna chlorophylls and carotenoids capture sunlight and transfer the resulting excitation energy to the photosynthetic reaction center (PRC). Small reorganization energy, λ and well-balanced electronic coupling between donors and acceptors in the PRC favor formation of a highly efficient charge-separated (CS) state. By covalently linking electron/energy donors to acceptors, organic molecular dyads and triads that mimic natural photosynthesis were synthesized and studied. Peripherally linked free base phthalocyanine (Pc)-fullerene (C60) and a zinc (Zn) phthalocyanine-C60 dyads were synthesized. Photoexcitation of the Pc moiety resulted in singlet-singlet energy transfer to the attached C60, followed by electron transfer. The lifetime of the CS state was 94 ps. Linking C60 axially to silicon (Si) Pc, a lifetime of the CS state of 4.5 ns was realized. The exceptionally long-lived CS state of the SiPc-C60 dyad qualifies it for applications in solar energy conversion devices. A secondary electron donor was linked to the dyad to obtain a carotenoid (Car)-SiPc-C60 triad and ferrocene (Fc)-SiPc-C60 triad. Excitation of the SiPc moiety resulted in fast electron transfer from the Car or Fc secondary electron donors to the C60. The lifetime of the CS state was 17 ps and 1.2 ps in Car-SiPc-C60 and Fc-SiPc-C60, respectively. In Chapter 3, an efficient synthetic route that yielded regioselective oxidative porphyrin dimerization is presented. Using Cu2+ as the oxidant, meso-β doubly-connected fused porphyrin dimers were obtained in very high yields. Removal of the copper from the macrocycle affords a free base porphyrin dimer. This allows for exchange of metals and provides a route to a wider range of metallporphyrin dimers. In Chapter 4, the development of an efficient and an expedient route to bacteriopurpurin synthesis is discussed. Meso-10,20- diformylation of porphyrin was achieved and one-pot porphyrin diacrylate synthesis and cyclization to afford bacteriopurpurin was realized. The bacteriopurpurin had a reduction potential of - 0.85 V vs SCE and λmax, 845 nm.
ContributorsArero, Jaro (Author) / Gust, Devens (Thesis advisor) / Moore, Ana (Committee member) / Gould, Ian (Committee member) / Arizona State University (Publisher)
Created2014