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 80
Description
Manufacture of building materials requires significant energy, and as demand for these materials continues to increase, the energy requirement will as well. Offsetting this energy use will require increased focus on sustainable building materials. Further, the energy used in building, particularly in heating and air conditioning, accounts for 40 percent of a buildings energy use. Increasing the efficiency of building materials will reduce energy usage over the life time of the building. Current methods for maintaining the interior environment can be highly inefficient depending on the building materials selected. Materials such as concrete have low thermal efficiency and have a low heat capacity meaning it provides little insulation. Use of phase change materials (PCM) provides the opportunity to increase environmental efficiency of buildings by using the inherent latent heat storage as well as the increased heat capacity. Incorporating PCM into concrete via lightweight aggregates (LWA) by direct addition is seen as a viable option for increasing the thermal storage capabilities of concrete, thereby increasing building energy efficiency. As PCM change phase from solid to liquid, heat is absorbed from the surroundings, decreasing the demand on the air conditioning systems on a hot day or vice versa on a cold day. Further these materials provide an additional insulating capacity above the value of plain concrete. When the temperature drops outside the PCM turns back into a solid and releases the energy stored from the day. PCM is a hydrophobic material and causes reductions in compressive strength when incorporated directly into concrete, as shown in previous studies. A proposed method for mitigating this detrimental effect, while still incorporating PCM into concrete is to encapsulate the PCM in aggregate. This technique would, in theory, allow for the use of phase change materials directly in concrete, increasing the thermal efficiency of buildings, while negating the negative effect on compressive strength of the material.
ContributorsSharma, Breeann (Author) / Neithalath, Narayanan (Thesis advisor) / Mobasher, Barzin (Committee member) / Rajan, Subramaniam D. (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
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
The main objective of this study is to investigate the mechanical behaviour of cementitious based composites subjected dynamic tensile loading, with effects of strain rate, temperature, addition of short fibres etc. Fabric pullout model and tension stiffening model based on finite difference model, previously developed at Arizona State University were used to help study the bonding mechanism between fibre and matrix, and the phenomenon of tension stiffening due to the addition of fibres and textiles. Uniaxial tension tests were conducted on strain-hardening cement-based composites (SHCC), textile reinforced concrete (TRC) with and without addition of short fibres, at the strain rates ranging from 25 s-1 to 100 s-1. Historical data on quasi-static tests of same materials were used to demonstrate the effects including increases in average tensile strength, strain capacity, work-to-fracture due to high strain rate. Polyvinyl alcohol (PVA), glass, polypropylene were employed as reinforcements of concrete. A state-of-the-art phantom v7 high speed camera was setup to record the video at frame rate of 10,000 fps. Random speckle pattern of texture style was made on the surface of specimens for image analysis. An optical non-contacting deformation measurement technique referred to as digital image correlation (DIC) method was used to conduct the image analysis by means of tracking the displacement field through comparison between the reference image and deformed images. DIC successfully obtained full-filed strain distribution, strain versus time responses, demonstrated the bonding mechanism from perspective of strain field, and corrected the stress-strain responses.
ContributorsYao, Yiming (Author) / Barzin, Mobasher (Thesis advisor) / Rajan, Subramaniam D. (Committee member) / Neithalath, Narayanan (Committee member) / Arizona State University (Publisher)
Created2013
Description
Properties of random porous material such as pervious concrete are strongly dependant on its pore structure features. This research deals with the development of an understanding of the relationship between the material structure and the mechanical and functional properties of pervious concretes. The fracture response of pervious concrete specimens proportioned for different porosities, as a function of the pore structure features and fiber volume fraction, is studied. Stereological and morphological methods are used to extract the relevant pore structure features of pervious concretes from planar images. A two-parameter fracture model is used to obtain the fracture toughness (KIC) and critical crack tip opening displacement (CTODc) from load-crack mouth opening displacement (CMOD) data of notched beams under three-point bending. The experimental results show that KIC is primarily dependent on the porosity of pervious concretes. For a similar porosity, an increase in pore size results in a reduction in KIC. At similar pore sizes, the effect of fibers on the post-peak response is more prominent in mixtures with a higher porosity, as shown by the residual load capacity, stress-crack extension relationships, and GR curves. These effects are explained using the mean free spacing of pores and pore-to-pore tortuosity in these systems. A sensitivity analysis is employed to quantify the influence of material design parameters on KIC. This research has also focused on studying the relationship between permeability and tortuosity as it pertains to porosity and pore size of pervious concretes. Various ideal geometric shapes were also constructed that had varying pore sizes and porosities. The pervious concretes also had differing pore sizes and porosities. The permeabilities were determined using three different methods; Stokes solver, Lattice Boltzmann method and the Katz-Thompson equation. These values were then compared to the tortuosity values determined using a Matlab code that uses a pore connectivity algorithm. The tortuosity was also determined from the inverse of the conductivity determined from a numerical analysis that was necessary for using the Katz-Thompson equation. These tortuosity values were then compared to the permeabilities. The pervious concretes and ideal geometric shapes showed consistent similarities betbetween their tortuosities and permeabilities.
ContributorsRehder, Benjamin (Author) / Neithalath, Narayanana (Thesis advisor) / Mobasher, Barzin (Committee member) / Rajan, Subramaniam D. (Committee member) / Arizona State University (Publisher)
Created2013
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
The focus of this investigation is on the optimum placement of a limited number of dampers, fewer than the number of blades, on a bladed disk to induce the smallest amplitude of blade response. The optimization process considers the presence of random mistuning, i.e. small involuntary variations in blade stiffness properties resulting, say, from manufacturing variability. Designed variations of these properties, known as intentional mistuning, is considered as an option to reduce blade response and the pattern of two blade types (A and B blades) is then part of the optimization in addition to the location of dampers on the disk. First, this study focuses on the formulation and validation of dedicated algorithms for the selection of the damper locations and the intentional mistuning pattern. Failure of one or several of the dampers could lead to a sharp rise in blade response and this issue is addressed by including, in the optimization, the possibility of damper failure to yield a fail-safe solution. The high efficiency and accuracy of the optimization algorithms is assessed in comparison with computationally very demanding exhaustive search results. Second, the developed optimization algorithms are applied to nonlinear dampers (underplatform friction dampers), as well as to blade-blade dampers, both linear and nonlinear. Further, the optimization of blade-only and blade-blade linear dampers is extended to include uncertainty or variability in the damper properties induced by manufacturing or wear. It is found that the optimum achieved without considering such uncertainty is robust with respect to it. Finally, the potential benefits of using two different types of friction dampers differing in their masses (A and B types), on a bladed disk are considered. Both A/B pattern and the damper masses are optimized to obtain the largest benefit compared to using identical dampers of optimized masses on every blade. Four situations are considered: tuned disks, disks with random mistuning of blade stiffness, and, disks with random mistuning of both blade stiffness and damper normal forces with and without damper variability induced by manufacturing and wear. In all cases, the benefit of intentional mistuning of friction dampers is small, of the order of a few percent.
ContributorsMurthy, Raghavendra Narasimha (Author) / Mignolet, Marc P (Thesis advisor) / Rajan, Subramaniam D. (Committee member) / Lentz, Jeff (Committee member) / Chattopadhyay, Aditi (Committee member) / Jiang, Hanqing (Committee member) / Arizona State University (Publisher)
Created2012
Description
The main objective of this study is to develop an innovative system in the form of a sandwich panel type composite with textile reinforced skins and aerated concrete core. Existing theoretical concepts along with extensive experimental investigations were utilized to characterize the behavior of cement based systems in the presence of individual fibers and textile yarns. Part of this thesis is based on a material model developed here in Arizona State University to simulate experimental flexural response and back calculate tensile response. This concept is based on a constitutive law consisting of a tri-linear tension model with residual strength and a bilinear elastic perfectly plastic compression stress strain model. This parametric model was used to characterize Textile Reinforced Concrete (TRC) with aramid, carbon, alkali resistant glass, polypropylene TRC and hybrid systems of aramid and polypropylene. The same material model was also used to characterize long term durability issues with glass fiber reinforced concrete (GFRC). Historical data associated with effect of temperature dependency in aging of GFRC composites were used. An experimental study was conducted to understand the behavior of aerated concrete systems under high stain rate impact loading. Test setup was modeled on a free fall drop of an instrumented hammer using three point bending configuration. Two types of aerated concrete: autoclaved aerated concrete (AAC) and polymeric fiber-reinforced aerated concrete (FRAC) were tested and compared in terms of their impact behavior. The effect of impact energy on the mechanical properties was investigated for various drop heights and different specimen sizes. Both materials showed similar flexural load carrying capacity under impact, however, flexural toughness of fiber-reinforced aerated concrete was proved to be several degrees higher in magnitude than that provided by plain autoclaved aerated concrete. Effect of specimen size and drop height on the impact response of AAC and FRAC was studied and discussed. Results obtained were compared to the performance of sandwich beams with AR glass textile skins with aerated concrete core under similar impact conditions. After this extensive study it was concluded that this type of sandwich composite could be effectively used in low cost sustainable infrastructure projects.
ContributorsDey, Vikram (Author) / Mobasher, Barzin (Thesis advisor) / Rajan, Subramaniam D. (Committee member) / Neithalath, Narayanan (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