Matching Items (78)
Description
Methods to test hypotheses of mediated effects in the pretest-posttest control group design are understudied in the behavioral sciences (MacKinnon, 2008). Because many studies aim to answer questions about mediating processes in the pretest-posttest control group design, there is a need to determine which model is most appropriate to test hypotheses about mediating processes and what happens to estimates of the mediated effect when model assumptions are violated in this design. The goal of this project was to outline estimator characteristics of four longitudinal mediation models and the cross-sectional mediation model. Models were compared on type 1 error rates, statistical power, accuracy of confidence interval coverage, and bias of parameter estimates. Four traditional longitudinal models and the cross-sectional model were assessed. The four longitudinal models were analysis of covariance (ANCOVA) using pretest scores as a covariate, path analysis, difference scores, and residualized change scores. A Monte Carlo simulation study was conducted to evaluate the different models across a wide range of sample sizes and effect sizes. All models performed well in terms of type 1 error rates and the ANCOVA and path analysis models performed best in terms of bias and empirical power. The difference score, residualized change score, and cross-sectional models all performed well given certain conditions held about the pretest measures. These conditions and future directions are discussed.
ContributorsValente, Matthew John (Author) / MacKinnon, David (Thesis advisor) / West, Stephen (Committee member) / Aiken, Leona (Committee member) / Enders, Craig (Committee member) / Arizona State University (Publisher)
Created2015
Description
The current study utilized data from two longitudinal samples to test mechanisms in the relation between a polygenic risk score indexing serotonin functioning and alcohol use in adolescence. Specifically, this study tested whether individuals with lower levels of serotonin functioning as indexed by a polygenic risk score were vulnerable to poorer self-regulation, and whether poorer self-regulation subsequently predicted the divergent outcomes of depressive symptoms and aggressive/antisocial behaviors. This study then examined whether depressive symptoms and aggressive/antisocial behaviors conferred risk for later alcohol use in adolescence, and whether polygenic risk and effortful control had direct effects on alcohol use that were not mediated through problem behaviors. Finally, the study examined the potential moderating role of gender in these pathways to alcohol use.
Structural equation modeling was used to test hypotheses. Results from an independent genome-wide association study of 5-hydroxyindoleacetic acid in the cerebrospinal fluid were used to create serotonin (5-HT) polygenic risk scores, wherein higher scores reflected lower levels of 5-HT functioning. Data from three time points were drawn from each sample, and all paths were prospective. Findings suggested that 5-HT polygenic risk did not predict self-regulatory constructs. However, 5-HT polygenic risk did predict the divergent outcomes of depression and aggression/antisociality, such that higher levels of 5-HT polygenic risk predicted greater levels of depression and aggression/antisociality. Results most clearly supported adolescents’ aggression/antisociality as a mechanism in the relation between 5-HT polygenic risk and later alcohol use. Deficits in self-regulation also predicted depression and aggression/antisociality, and indirectly predicted alcohol use through aggression/antisociality. These pathways to alcohol use might be the most salient for boys with low levels of socioeconomic status.
Results are novel contributions to the literature. The previously observed association between serotonin functioning and alcohol use might be due, in part, to the fact that individuals with lower levels of serotonin functioning are predisposed towards developing earlier aggression/antisociality. Results did not support the hypothesis that serotonin functioning predisposes individuals to deficits in self-regulatory abilities. Findings extend previous research by suggesting that serotonin functioning and self-regulation might be transdiagnostic risk factors for many types of psychopathology.
Structural equation modeling was used to test hypotheses. Results from an independent genome-wide association study of 5-hydroxyindoleacetic acid in the cerebrospinal fluid were used to create serotonin (5-HT) polygenic risk scores, wherein higher scores reflected lower levels of 5-HT functioning. Data from three time points were drawn from each sample, and all paths were prospective. Findings suggested that 5-HT polygenic risk did not predict self-regulatory constructs. However, 5-HT polygenic risk did predict the divergent outcomes of depression and aggression/antisociality, such that higher levels of 5-HT polygenic risk predicted greater levels of depression and aggression/antisociality. Results most clearly supported adolescents’ aggression/antisociality as a mechanism in the relation between 5-HT polygenic risk and later alcohol use. Deficits in self-regulation also predicted depression and aggression/antisociality, and indirectly predicted alcohol use through aggression/antisociality. These pathways to alcohol use might be the most salient for boys with low levels of socioeconomic status.
Results are novel contributions to the literature. The previously observed association between serotonin functioning and alcohol use might be due, in part, to the fact that individuals with lower levels of serotonin functioning are predisposed towards developing earlier aggression/antisociality. Results did not support the hypothesis that serotonin functioning predisposes individuals to deficits in self-regulatory abilities. Findings extend previous research by suggesting that serotonin functioning and self-regulation might be transdiagnostic risk factors for many types of psychopathology.
ContributorsWang, Frances Lynn (Author) / Chassin, Laurie (Thesis advisor) / Eisenberg, Nancy (Committee member) / Lemery-Chalfant, Kathryn (Committee member) / MacKinnon, David (Committee member) / Arizona State University (Publisher)
Created2017
Description
The process of combining data is one in which information from disjoint datasets sharing at least a number of common variables is merged. This process is commonly referred to as data fusion, with the main objective of creating a new dataset permitting more flexible analyses than the separate analysis of each individual dataset. Many data fusion methods have been proposed in the literature, although most utilize the frequentist framework. This dissertation investigates a new approach called Bayesian Synthesis in which information obtained from one dataset acts as priors for the next analysis. This process continues sequentially until a single posterior distribution is created using all available data. These informative augmented data-dependent priors provide an extra source of information that may aid in the accuracy of estimation. To examine the performance of the proposed Bayesian Synthesis approach, first, results of simulated data with known population values under a variety of conditions were examined. Next, these results were compared to those from the traditional maximum likelihood approach to data fusion, as well as the data fusion approach analyzed via Bayes. The assessment of parameter recovery based on the proposed Bayesian Synthesis approach was evaluated using four criteria to reflect measures of raw bias, relative bias, accuracy, and efficiency. Subsequently, empirical analyses with real data were conducted. For this purpose, the fusion of real data from five longitudinal studies of mathematics ability varying in their assessment of ability and in the timing of measurement occasions was used. Results from the Bayesian Synthesis and data fusion approaches with combined data using Bayesian and maximum likelihood estimation methods were reported. The results illustrate that Bayesian Synthesis with data driven priors is a highly effective approach, provided that the sample sizes for the fused data are large enough to provide unbiased estimates. Bayesian Synthesis provides another beneficial approach to data fusion that can effectively be used to enhance the validity of conclusions obtained from the merging of data from different studies.
ContributorsMarcoulides, Katerina M (Author) / Grimm, Kevin (Thesis advisor) / Levy, Roy (Thesis advisor) / MacKinnon, David (Committee member) / Suk, Hye Won (Committee member) / Arizona State University (Publisher)
Created2017
Description
Microplastics are emerging to be major problem when it comes to water pollution and they pose a great threat to marine life. These materials have the potential to affect a wide range of human population since humans are the major consumers of marine organisms. Microplastics are less than 5 mm in diameter, and can escape from traditional wastewater treatment plant (WWTP) processes and end up in our water sources. Due to their small size, they have a large surface area and can react with chlorine, which it encounters in the final stages of WWTP. After the microplastics accumulate in various bodies of water, they are exposed to sunlight, which contains oxidative ultraviolet (UV) light. Since the microplastics are exposed to oxidants during and after the treatment, there is a strong chance that they will undergo chemical and/or physical changes. The WWTP conditions were replicated in the lab by varying the concentrations of chlorine from 70 to 100 mg/L in increments of 10 mg/L and incubating the samples in chlorine baths for 1–9 days. The chlorinated samples were tested for any structural changes using Raman spectroscopy. High density polyethylene (HDPE), polystyrene (PS), and polypropylene (PP) were treated in chlorine baths and observed for Raman intensity variations, Raman peak shifts, and the formation of new peaks over different exposure times. HDPE responded with a lot of oxidation peaks and shifts of peaks after just one day. For the degradation of semi-crystalline polymers, there was a reduction in crystallinity, as verified by thermal analysis. There was a decrease in the enthalpy of melting as well as the melting temperature with an increase in the exposure time or chlorine concentration, which pointed at the degradation of plastics and bond cleavages. To test the plastic response to
ii
UV, the samples were exposed to sunlight for up to 210 days and analyzed under Raman spectroscopy. Overall the physical and chemical changes with the polymers are evident and makes a way for the wastewater treatment plant to take necessary steps to capture the microplastics to avoid the release of any kind of degraded microplastics that could affect marine life and the environment.
ii
UV, the samples were exposed to sunlight for up to 210 days and analyzed under Raman spectroscopy. Overall the physical and chemical changes with the polymers are evident and makes a way for the wastewater treatment plant to take necessary steps to capture the microplastics to avoid the release of any kind of degraded microplastics that could affect marine life and the environment.
ContributorsKelkar, Varun (Author) / Green, Matthew D (Thesis advisor) / Tongay, Sefaattin (Committee member) / Halden, Rolf U. (Committee member) / Arizona State University (Publisher)
Created2017
Description
A new class of layered materials called the transition metal trichalcogenides (TMTCs) exhibit strong anisotropic properties due to their quasi-1D nature. These 2D materials are composed of chain-like structures which are weakly bound to form planar sheets with highly directional properties. The vibrational properties of three materials from the TMTC family, specifically TiS3, ZrS3, and HfS3, are relatively unknown and studies performed in this work elucidates the origin of their Raman characteristics. The crystals were synthesized through chemical vapor transport prior to mechanical exfoliation onto Si/SiO¬2 substrates. XRD, AFM, and Raman spectroscopy were used to determine the crystallinity, thickness, and chemical signature of the exfoliated crystals. Vibrational modes and anisotropic polarization are investigated through density functional theory calculations and angle-resolved Raman spectroscopy. Particular Raman modes are explored in order to correlate select peaks to the b-axis crystalline direction. Mode III vibrations for TiS3, ZrS3, and HfS3 are shared between each material and serves as a unique identifier of the crystalline orientation in MX3 materials. Similar angle-resolved Raman studies were conducted on the novel Nb0.5Ti0.5S3 alloy material grown through chemical vapor transport. Results show that the anisotropy direction is more difficult to determine due to the randomization of quasi-1D chains caused by defects that are common in 2D alloys. This work provides a fundamental understanding of the vibrational properties of various TMTC materials which is needed to realize applications in direction dependent polarization and linear dichroism.
ContributorsKong, Wilson (Author) / Tongay, Sefaattin (Thesis advisor) / Wang, Liping (Committee member) / Green, Matthew (Committee member) / Arizona State University (Publisher)
Created2017
Description
Since the discovery of graphene, two dimensional materials (2D materials) have become a focus of interest for material research due to their many unique physical properties embedded in their 2D structure. While they host many exciting potential applications, some of these 2D materials are subject to environmental instability issues induced by interaction between material and gas molecules in air, which poses a barrier to further application and manufacture. To overcome this, it is necessary to understand the origin of material instability and interaction with molecules commonly found in air, as well as developing a reproducible and manufacturing compatible method to post-process these materials to extend their lifetime. In this work, the very first investigation on environmental stability on Te containing anisotropic 2D materials such as GaTe and ZrTe3 is reported. Experimental results have demonstrated that freshly exfoliated GaTe quickly deteriorate in air, during which the Raman spectrum, surface morphology, and surface chemistry undergo drastic changes. Environmental Raman spectroscopy and XPS measurements demonstrate that H2O molecules in air interact strongly on the surface while O2, N2, and inert gases don't show any detrimental effects on GaTe surface. Moreover, the anisotropic properties of GaTe slowly disappear during the aging process. To prevent this gas/material interaction based surface transformation, diazonium based surface functionalization is adopted on these Te based 2D materials. Environmental Raman spectroscopy results demonstrate that the stability of functionalized Te based 2D materials exhibit much higher stability both in ambient and extreme conditions. Meanwhile, PL spectroscopy, angle resolved Raman spectroscopy, atomic force microscopy measurements confirm that many attractive physical properties of the material are not affected by surface functionalization. Overall, these findings unveil the degradation mechanism of Te based 2D materials as well as provide a way to significantly enhance their environmental stability through an inexpensive and reproducible surface chemical functionalization route.
ContributorsYang, Sijie (Author) / Tongay, Sefaattin (Thesis advisor) / Gould, Ian (Thesis advisor) / Trovitch, Ryan (Committee member) / Ghirlanda, Giovanna (Committee member) / Arizona State University (Publisher)
Created2017
Description
Photocatalytic activity of titanium dioxide (titania or TiO2) offers enormous potential in solving energy and environmental problems. Immobilization of titania nanoparticles on inert substrates is an effective way of utilizing its photocatalytic activity since nanoparticles enable high mass-transport, and immobilization avoids post-treatment separation. For competitive photocatalytic performance, the morphology of the substrate can be engineered to enhance mass-transport and light accessibility. In this work, two types of fiber architectures (i.e., dispersed polymer/titania phase or D-phase, and multi-phase polymer-core/composite-shell fibers or M-phase) were explored as effective substrate solutions for anchoring titania. These fibers were fabricated using a low-cost and scalable fiber spinning technique. Polymethyl methacrylate (PMMA) was selected as the substrate material due to its ultraviolet (UV) transparency and stability against oxidative radicals. The work systematically investigates the influence of the fiber porosity on mass-transport and UV light scattering. The properties of the fabricated fiber systems were characterized by scanning electron microscopy (SEM), Brunauer–Emmett–Teller (BET), UV-vis spectrophotometry (UV-vis), and mechanical analysis. The photocatalytic performance was characterized by monitoring the decomposition of methylene blue (MB) under UV (i.e., 365 nm) light. Fabrication of photocatalytic support structures was observed to be an optimization problem where porosity improved mass transport but reduced UV accessibility. The D-phase fibers demonstrated the highest MB degradation rate (i.e., 0.116 min-1) due to high porosity (i.e., 33.2 m2/g). The M-phase fibers reported a better degradation rate compared to a D-phase fibers due to higher UV accessibility efficiency.
ContributorsKanth, Namrata (Author) / Song, Kenan (Thesis advisor) / Tongay, Sefaattin (Thesis advisor) / Kannan, Arunachala Mada (Committee member) / Arizona State University (Publisher)
Created2020
Description
Metal-organic frameworks have made a feature in the cutting-edge technology with a wide variety of applications because they are the new material candidate as adsorbent or membrane with high surface area, various pore sizes, and highly tunable framework functionality properties. The emergence of two-dimensional (2D) metal-organic frameworks has surged an outburst of intense research to understand the feasible synthesis and exciting material properties of these class of materials. Despite their potential, studies to date show that it is extremely challenging to synthesize and manufacture 2D MOF at large scales with ultimate control over crystallinity and thickness.
The field of research to date has produced various synthesis routes which can further be used to design 2D materials with a range of organic ligands and metal linkers. This thesis seeks to extend these design rules to demonstrate the competitive growth of two- dimensional (2D) metal-organic frameworks(MOF) and their alloys to predict which ligands and metals can be combined, study the intercalation of Bromine in these frameworks and their alloys which leads to the discovery of reduced band gap in the layered MOF alloy.
In this study it has been shown that the key factor in achieving layered 2D MOFs and it relies on the use of carefully engineered ligands to terminate the out-of-plane sites on metal clusters thereby eliminating strong interlayer hydrogen bond formation.
The major contribution of pyridine is to replace interlayer hydrogen bonding or other weak chemical bonds. Overall results establish an entirely new synthesis method for producing highly crystalline and scalable 2D MOFs and their alloys. Bromine intercalation merits future studies on band gap engineering in these layered materials.
The field of research to date has produced various synthesis routes which can further be used to design 2D materials with a range of organic ligands and metal linkers. This thesis seeks to extend these design rules to demonstrate the competitive growth of two- dimensional (2D) metal-organic frameworks(MOF) and their alloys to predict which ligands and metals can be combined, study the intercalation of Bromine in these frameworks and their alloys which leads to the discovery of reduced band gap in the layered MOF alloy.
In this study it has been shown that the key factor in achieving layered 2D MOFs and it relies on the use of carefully engineered ligands to terminate the out-of-plane sites on metal clusters thereby eliminating strong interlayer hydrogen bond formation.
The major contribution of pyridine is to replace interlayer hydrogen bonding or other weak chemical bonds. Overall results establish an entirely new synthesis method for producing highly crystalline and scalable 2D MOFs and their alloys. Bromine intercalation merits future studies on band gap engineering in these layered materials.
ContributorsVijay, Shiljashree (Author) / Tongay, Sefaattin (Thesis advisor) / Green, Matthew D (Committee member) / Zhuang, Houlong (Committee member) / Arizona State University (Publisher)
Created2020
Description
Losses in commercial microwave dielectrics arise from spin excitations in paramagnetic transition metal dopants, at least at reduced temperatures. The magnitude of the loss tangent can be altered by orders of magnitude through the application of an external magnetic field. The goal of this thesis is to produce “smart” dielectrics that can be switched “on” or “off” at small magnetic fields while investigating the influence of transition metal dopants on the dielectric, magnetic, and structural properties.
A proof of principle demonstration of a resonator that can switch from a high-Q “on state” to a low-Q “off state” at reduced temperatures is demonstrated in (Al1-xFex)2O3 and La(Al1-xFex)O3. The Fe3+ ions are in a high spin state (S=5/2) and undergo electron paramagnetic resonance absorption transitions that increase the microwave loss of the system. Transitions occur between mJ states with a corresponding change in the angular momentum, J, by ±ħ (i.e., ΔmJ=±1) at small magnetic fields. The paramagnetic ions also have an influence on the dielectric and magnetic properties, which I explore in these systems along with another low loss complex perovskite material, Ca[(Al1-xFex)1/2Nb1/2]O3. I describe what constitutes an optimal microwave loss switchable material induced from EPR transitions and the mechanisms associated with the key properties.
As a first step to modeling the properties of high-performance microwave host lattices and ultimately their performance at microwave frequencies, a first-principles approach is used to determine the structural phase stability of various complex perovskites with a range of tolerance factors at 0 K and finite temperatures. By understanding the correct structural phases of these complex perovskites, the temperature coefficient of resonant frequency can be better predicted.
A strong understanding of these parameters is expected to open the possibility to produce new types of high-performance switchable filters, time domain MIMO’s, multiplexers, and demultiplexers.
A proof of principle demonstration of a resonator that can switch from a high-Q “on state” to a low-Q “off state” at reduced temperatures is demonstrated in (Al1-xFex)2O3 and La(Al1-xFex)O3. The Fe3+ ions are in a high spin state (S=5/2) and undergo electron paramagnetic resonance absorption transitions that increase the microwave loss of the system. Transitions occur between mJ states with a corresponding change in the angular momentum, J, by ±ħ (i.e., ΔmJ=±1) at small magnetic fields. The paramagnetic ions also have an influence on the dielectric and magnetic properties, which I explore in these systems along with another low loss complex perovskite material, Ca[(Al1-xFex)1/2Nb1/2]O3. I describe what constitutes an optimal microwave loss switchable material induced from EPR transitions and the mechanisms associated with the key properties.
As a first step to modeling the properties of high-performance microwave host lattices and ultimately their performance at microwave frequencies, a first-principles approach is used to determine the structural phase stability of various complex perovskites with a range of tolerance factors at 0 K and finite temperatures. By understanding the correct structural phases of these complex perovskites, the temperature coefficient of resonant frequency can be better predicted.
A strong understanding of these parameters is expected to open the possibility to produce new types of high-performance switchable filters, time domain MIMO’s, multiplexers, and demultiplexers.
ContributorsGonzales, Justin Michael (Author) / Newman, Nathan (Thesis advisor) / Muhich, Christopher (Committee member) / Tongay, Sefaattin (Committee member) / Arizona State University (Publisher)
Created2020
Description
Transition metal di- and tri-halides (TMH) have recently gathered research attention owing to their intrinsic magnetism all the way down to their two-dimensional limit. 2D magnets, despite being a crucial component for realizing van der Waals heterostructures and devices with various functionalities, were not experimentally proven until very recently in 2017. The findings opened up enormous possibilities for studying new quantum states of matter that can enable potential to design spintronic, magnetic memory, data storage, sensing, and topological devices. However, practical applications in modern technologies demand materials with various physical and chemical properties such as electronic, optical, structural, catalytic, magnetic etc., which cannot be found within single material systems. Considering that compositional modifications in 2D systems lead to significant changes in properties due to the high anisotropy inherent to their crystallographic structure, this work focuses on alloying of TMH compounds to explore the potentials for tuning their properties. In this thesis, the ternary cation alloys of Co(1-x)Ni(x)Cl(2) and Mo(1-x)Cr(x)Cl(3) were synthesized via chemical vapor transport at a various stoichiometry. Their compositional, structural, and magnetic properties were studied using Energy Dispersive Spectroscopy, Raman Spectroscopy, X-Ray Diffraction, and Vibrating Sample Magnetometry. It was found that completely miscible ternary alloys of Co(1-x)Ni(x)Cl(2) show an increasing Néel temperature with nickel concentration. The Mo(1-x)Cr(x)Cl(3) alloy shows potential magnetic phase changes induced by the incorporation of molybdenum species within the host CrCl3 lattice. Magnetic measurements give insight into potential antiferromagnetic to ferromagnetic transition with molybdenum incorporation, accompanied by a shift in the magnetic easy-axis from parallel to perpendicular. Phase separation was found in the Fe(1-x)Cr(x)Cl(3) ternary alloy indicating that crystallographic structure compatibility plays an essential role in determining the miscibility of two parent compounds. Alloying across two similar (TMH) compounds appears to yield predictable results in properties as in the case of Co(1-x)Ni(x)Cl(2), while more exotic transitions, as in the case of Mo(1-x)Cr(x)Cl(3), can emerge by alloying dissimilar compounds. When dissimilarity reaches a certain limit, as with Fe(1-x)Cr(x)Cl(3), phase separation becomes more favorable. Future studies focusing on magnetic and structural phase transitions will reveal more insight into the effect of alloying in these TMH systems.
ContributorsKolari, Pranvera (Author) / Tongay, Sefaattin (Thesis advisor) / Jiao, Yang (Committee member) / Muhich, Christopher (Committee member) / Arizona State University (Publisher)
Created2020