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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

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
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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

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
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Objectives: Although childhood obesity has received growing attention, parents still fail to recognize overweight and obesity in their children. Accurate identification of overweight or obesity in their child is associated with the parent's responsiveness to interventions aimed at preventing weight-related health issues. Recent research shows that a child's age and

Objectives: Although childhood obesity has received growing attention, parents still fail to recognize overweight and obesity in their children. Accurate identification of overweight or obesity in their child is associated with the parent's responsiveness to interventions aimed at preventing weight-related health issues. Recent research shows that a child's age and gender are associated with parental misperception of their child's weight status, but little is known about the interaction of these factors across various age groups. This study examined the association between a wide range of parent, child, and household factors and the accuracy of parental perception of their child's body weight status compared to parent-measured body weight status. Methods: Data were collected from a random-digit-dial telephone survey of 1708 households located in five low-income New Jersey cities with large minority populations. A subset of 548 children whose parents completed the survey and returned a worksheet of parent-measured heights and weights were the focus of the analysis. Bivariate and multivariate analyses were performed to determine the factors significantly associated with parental perception of their child's body weight status. Results: Based on parent-measure heights and weights, 36% of the children were overweight or obese (OWOB). Only 21% of OWOB children were perceived by their parents as OWOB. Child gender, child body mass index (BMI) and parent BMI were significant independent predictors of parents' accuracy at perceiving their child's body weight status. Conclusion: Boys, OWOB children, and children of OWOB parents had significantly greater odds of parental underestimation of their body weight status. Parents had better recognition of OWOB in their daughters, especially older daughters, than in their sons, suggesting parental gender bias in identifying OWOB in children. Further research is needed regarding parental gender bias and its implications in OWOB identification in children.
ContributorsBader, Wendy (Author) / Ohri-Vachaspati, Punam (Thesis advisor) / Lloyd, Kristen (Committee member) / Crespo, Noe (Committee member) / Arizona State University (Publisher)
Created2013
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Objectives Through a cross-sectional observational study, this thesis evaluates the relationship between food insecurity and weight status, eating behaviors, the home food environment, meal planning and preparation, and perceived stress as it relates to predominantly Hispanic/Latino parents in Phoenix, Arizona. The purpose of this study was to address gaps in

Objectives Through a cross-sectional observational study, this thesis evaluates the relationship between food insecurity and weight status, eating behaviors, the home food environment, meal planning and preparation, and perceived stress as it relates to predominantly Hispanic/Latino parents in Phoenix, Arizona. The purpose of this study was to address gaps in the literature by examining differences in "healthy" and "unhealthy" eating behaviors, foods available in the home, how time and low energy impact meal preparation, and the level of stress between food security groups. Methods Parents, 18 years or older, were recruited during two pre-scheduled health fairs, from English as a second language classes, or from the Women, Infants, and Children's clinic at a local community center, Golden Gate Community Center, in Phoenix, Arizona. An interview, electronic, or paper survey were offered in either Spanish or English to collect data on the variables described above. In addition to the survey, height and weight were collected for all participants to determine BMI and weight status. One hundred and sixty participants were recruited. Multivariate linear and logistic regression models, adjusting for weight status, education, race/ethnicity, income level, and years residing in the U.S., were used to assess the relationship between food security status and weight status, eating behaviors, the home food environment, meal planning and preparation, and perceived stress. Results Results concluded that food insecurity was more prevalent among parents reporting lower income levels compared to higher income levels (p=0.017). In adjusted models, higher perceived cost of fruits (p=0.004) and higher perceived level of stress (p=0.001) were associated with food insecurity. Given that the sample population was predominately women, a post-hoc analysis was completed on women only. In addition to the two significant results noted in the adjusted analyses, the women-only analysis revealed that food insecure mothers reported lower amounts of vegetables served with meals (p=0.019) and higher use of fast-food when tired or running late (p=0.043), compared to food secure mothers. Conclusion Additional studies are needed to further assess differences in stress levels between food insecure parents and food insecure parents, with special consideration for directionality and its relationship to weight status.
ContributorsVillanova, Christina (Author) / Bruening, Meg (Thesis advisor) / Ohri-Vachaspati, Punam (Committee member) / Vega-Lopez, Sonia (Committee member) / Arizona State University (Publisher)
Created2014
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Fruit and vegetable (FV) consumption continues to lag far behind US Department of Agriculture (USDA) recommendations. Interventions targeting individuals' dietary behaviors address only a small fraction of dietary influences. Changing the food environment by increasing availability of and excitement for FV through local food production has shown promise as a

Fruit and vegetable (FV) consumption continues to lag far behind US Department of Agriculture (USDA) recommendations. Interventions targeting individuals' dietary behaviors address only a small fraction of dietary influences. Changing the food environment by increasing availability of and excitement for FV through local food production has shown promise as a method for enhancing intake. However, the extent to which local production is sufficient to meet recommended FV intakes, or actual intakes, of specific populations remains largely unconsidered. This study was the first of its kind to evaluate the capacity to support FV intake of Arizona's population with statewide production of FV. We created a model to evaluate what percentage of Dietary Guidelines for Americans (DGA) recommendations, as well as actual consumption, state-level FV production could meet in a given year. Intake and production figures were amended to include estimates of only fresh, non-tropical FV. Production was then estimated by month and season to illustrate fluctuations in availability of FV. Based on our algorithm, Arizona production met 184.5% of aggregate fresh vegetable recommendations, as well as 351.9% of estimated intakes of Arizonans, but met only 29.7% of recommended and 47.8% of estimated intake of fresh, non-tropical fruit. Much of the excess vegetable production can be attributed to the dark-green vegetable sub-group category, which could meet 3204.6% and 3160% of Arizonans' aggregated recommendations and estimated intakes, respectively. Only minimal seasonal variations in the total fruit and total vegetable categories were found, but production of the five vegetable sub-groups varied between the warm and cool seasons by 19-98%. For example, in the starchy vegetable group, cool season (October to March) production met only 3.6% of recommendations, but warm season (April to November) production supplied 196.5% of recommendations. Results indicate that Arizona agricultural production has the capacity to meet a large proportion of the population's FV needs throughout much of the year, while at the same time remaining a major producer of dark-green vegetables for out-of-state markets.
ContributorsVaudrin, Nicole (Author) / Wharton, Christopher (Christopher Mack), 1977- (Thesis advisor) / Bruening, Meg (Thesis advisor) / Ohri-Vachaspati, Punam (Committee member) / Villalobos, J. Rene (Committee member) / Arizona State University (Publisher)
Created2013
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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

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
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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

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
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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

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
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In recent years, overall consumption of meat products has been decreasing, and at the same time vegetarianism is on the rise. A variety of factors are likely driving changes in consumers' attitudes towards, and consumption of, meat products. Although concern regarding animal welfare may contribute to these trends, growing consumer

In recent years, overall consumption of meat products has been decreasing, and at the same time vegetarianism is on the rise. A variety of factors are likely driving changes in consumers' attitudes towards, and consumption of, meat products. Although concern regarding animal welfare may contribute to these trends, growing consumer interest in the roles that production and processing of meat play in terms of environmental degradation could also impact individuals' decisions about the inclusion of meat in their diets. Because these factors could be related to moral attitudes as well, the purpose of this study was to explore the relations among meat consumption, general environmental attitudes, and moral `foundations' of decision-making, including concern about minimizing `harm' and maximizing `care,' as well as issues of `purity' and `sanctity.' A survey was conducted among current college students using the New Ecological Paradigm scale and the Moral Foundations Questionnaire to assess environmental and moral attitudes. A food frequency questionnaire was used to assess meat consumption. Multiple linear regression analyses explored the relations of environmental and moral attitudes with meat consumption, controlling for potential confounding variables. The results showed no significant correlations among meat consumption, environmental attitudes or moral foundations of harm/care and purity/sanctity.
ContributorsSpringer, LeeAnn (Author) / Wharton, Christopher (Christopher Mack), 1977- (Thesis advisor) / Hekler, Eric (Thesis advisor) / Ohri-Vachaspati, Punam (Committee member) / Hall, Rick (Committee member) / Arizona State University (Publisher)
Created2013
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The body is capable of regulating hunger in several ways. Some of these hunger regulation methods are innate, such as genetics, and some, such as the responses to stress and to the smell of food, are innate but can be affected by body conditions such as BMI and physical activity.

The body is capable of regulating hunger in several ways. Some of these hunger regulation methods are innate, such as genetics, and some, such as the responses to stress and to the smell of food, are innate but can be affected by body conditions such as BMI and physical activity. Further, some hunger regulation methods stem from learned behaviors originating from cultural pressures or parenting styles. These latter regulation methods for hunger can be grouped into the categories: emotion, environment, and physical. The factors that regulate hunger can also influence the incidence of disordered eating, such as eating in the absence of hunger (EAH). Eating in the absence of hunger can occur in one of two scenarios, continuous EAH or beginning EAH. College students are at a particularly high risk for EAH and weight gain due to stress, social pressures, and the constant availability of energy dense and nutrient poor food options. The purpose of this study is to validate a modified EAH-C survey in college students and to discover which of the three latent factors (emotion, environment, physical) best predicts continual and beginning EAH. To do so, a modified EAH-C survey, with additional demographic components, was administered to students at a major southwest university. This survey contained two questions, one each for continuing and beginning EAH, regarding 14 factors related to emotional, physical, or environmental reasons that may trigger EAH. The results from this study revealed that the continual and beginning EAH surveys displayed good internal consistency reliability. We found that for beginning and continuing EAH, although emotion is the strongest predictor of EAH, all three latent factors are significant predictors of EAH. In addition, we found that environmental factors had the greatest influence on an individual's likelihood to continue to eat in the absence of hunger. Due to statistical abnormalities and differing numbers of factors in each category, we were unable to determine which of the three factors exerted the greatest influence on an individual's likelihood to begin eating in the absence of hunger. These results can be utilized to develop educational tools aimed at reducing EAH in college students, and ultimately reducing the likelihood for unhealthy weight gain and health complications related to obesity.
ContributorsGoett, Taylor (Author) / Johnston, Carol (Thesis advisor) / Lee, Chong (Committee member) / Lespron, Christy (Committee member) / Arizona State University (Publisher)
Created2013