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- All Subjects: Chemistry
- Creators: Arizona State University
- Member of: ASU Electronic Theses and Dissertations
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
This thesis explores the extent to which entrepreneurship is possible for women in Saudi Arabia, and it's potential to increase Saudi women's socio-cultural autonomy, financial independence, and overall well-being. The study uses interviews and an online surveys to gather information from recognized female entrepreneurs, those officially registered with the Women's Business Center in Alkhober, Saudi Arabia, about how they founded their businesses, the challenges they have experienced, and the effects of business ownership. These women are interesting because their experience seems to run counter to Saudi society, which generally restricts women's activities. The study's findings show that despite their successes, Arab traditions still hinder the success of Alkhober female entrepreneurs, for instance, by requiring male guardianship and prohibiting travel unaccompanied by a man. From an institutional perspective, administrative and legal requirement can prevent women from fully realizing their potential as businesswomen. The existing women's rights legislation lacks authority because political opportunities for Alkhober women are still limited. For Saudi women entrepreneurship remains an alternative to joblessness and dissatisfaction derived from other employment sources. The challenges women entrepreneurs experience while starting businesses are lack of support from the executive branch of government, lack of quality education, and lack of available financial resources, in addition to the cultural barriers caused by Arab traditions restricting the activities of women. However, a key finding from this study is that the women interviewed all showed a high level of resourcefulness and creativity that helped them to circumvent such obstacles. This study recommends that the government provide financial services, or training programs to aspiring female entrepreneurs and offer incentives for women to register their businesses. This will benefit not just Saudi women but for the Saudi economy overall.
ContributorsAlhabidi, Mariam (Author) / C. Parmentier, Mary Jane C. Parmentier Jane (Thesis advisor) / Grossman, Gary M. (Committee member) / Crewe, Katherine (Committee member) / Arizona State University (Publisher)
Created2013
Description
Fibromyalgia (FM) is a chronic pain condition characterized by debilitating fatigue. This study examined the dynamic relation between interpersonal enjoyment and fatigue in 102 partnered and 74 unpartnered women with FM. Participants provided three daily ratings for 21 days. They rated their fatigue in late morning and at the end of the day. Both partnered and unpartnered participants reported their interpersonal enjoyment in the combined familial, friendship, and work domains (COMBINED domain) in the afternoon. Additionally, partnered participants reported their interpersonal enjoyment in the spousal domain. The study was guided by three hypotheses at the within-person level, based on daily diaries: (1) elevated late morning fatigue would predict diminished afternoon interpersonal enjoyment; (2) diminished interpersonal enjoyment would predict elevated end-of-day fatigue; (3) interpersonal enjoyment would mediate the late morning to end-of-day fatigue relationship. In cross-level models, the study explored whether individual differences (between-person) in late morning fatigue and afternoon interpersonal enjoyment would moderate within-person relations from late morning fatigue to afternoon interpersonal enjoyment, and from afternoon interpersonal enjoyment to end-of-day fatigue. Furthermore, it explored whether the hypothesized relationships at the within-person level would also emerge at the between-person level (between-person mediation models). Multilevel structural equation modeling and multilevel modeling were employed for model testing, separately for partnered and unpartnered participants. Within-person mediation models supported that on high fatigue mornings, afternoon interpersonal enjoyment was dampened in the spousal and combined domains in partnered and unpartnered samples. Moreover, low afternoon interpersonal enjoyment in both the spousal and combined domains predicted elevated end-of-day fatigue. Afternoon interpersonal enjoyment mediated the relationship of late morning to end-of-day fatigue in the combined domain but in not the spousal domain. Cross-level moderation analyses showed that individual differences in afternoon spousal enjoyment moderated the day-to-day relation between afternoon spousal enjoyment and end-of-day fatigue. Finally, the mediational chain was not observed at the between-person level. These findings suggest that preserving interpersonal enjoyment in non-spousal relations limits within-day increases in FM fatigue. They highlight the importance of examining domain-specificity in interpersonal enjoyment when studying fatigue, and suggest that targeting enjoyment in social relations may improve the efficacy of existing treatments.
ContributorsYeung, Wan (Author) / Aiken, Leona S. (Thesis advisor) / Davis, Mary C. (Thesis advisor) / Mackinnon, David P (Committee member) / Zautra, Alex J (Committee member) / Arizona State University (Publisher)
Created2013
Description
The connection between Hollywood costume design and the films of the 007/James Bond franchise, especially in regards to the changing perspective of the “Bond Girl”, is an intricate relationship that has previously been little researched. In the most recent Bond films, in particular, the female characters have become more powerful than the early characters and their roles within the narratives have changed with their characters taking on stronger and more integral roles. This thesis seeks to examine the films of the 007/James Bond franchise and how the rhetoric of the franchise’s costume design affects the representation of femininity and power in regards to the Bond Girls. After an overview of Bond history and costume theory, two films are analyzed as case studies: Dr. No (1962) which marks the beginning of the film franchise and Casino Royale (2006), which marks the more recent turn the films have taken. This thesis examines how the representations of Bond Girls and the use of costume design for their characters have changed over the course of the franchise from the days of Sean Connery to the recent reboot of the franchise with Daniel Craig as 007 James Bond. In addition to an examination of Bond Girl costume design, this thesis considers the role and influence of the costume designers. A designer’s vision of a character is derived from both the writing and the physical features of the actresses before them. Here this thesis considers how the rhetorical choices made by designers have contributed to an understanding of the relationship between femininity and power. Finally it shows how the costumes effect the power of the female characters and how the Bond Girls of today (Casino Royale) compare and/or contrast to Bond Girls of the past (Dr. No). This thesis combines the areas of feminist film theory and costume theory to provide an original rhetorical analysis of the Bond series in relation to costume design and examines the rhetorical statements made by the costume designers in their designs for the characters and how those statements influence the representations of the characters.
ContributorsSeverson, Andrea (Author) / Goggin, Maureen (Thesis advisor) / Ore, Ersula (Committee member) / Lamp, Kathleen (Committee member) / Arizona State University (Publisher)
Created2013
Description
In a conscious effort to combat the low enrollment of women in construction management, a program was created to retain women through a mentorship program - Advancing Women in Construction. A qualitative analysis, facilitated through a grounded theory approach, sought to understand if the program was indeed successful, and what value did the students derive from the programs and participating in the mentoring process.
ContributorsEicher, Matthew (Author) / Wilkinson, Christine Kajikawa (Thesis advisor) / Calleroz-White, Mistalene (Committee member) / Gibson, Jr., G. Edward (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
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