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Description
Pathogenic Gram-negative bacteria employ a variety of molecular mechanisms to combat host defenses. Two-component regulatory systems (TCR systems) are the most ubiquitous signal transduction systems which regulate many genes required for virulence and survival of bacteria. In this study, I analyzed different TCR systems in two clinically-relevant Gram-negative bacteria, i.e.,

Pathogenic Gram-negative bacteria employ a variety of molecular mechanisms to combat host defenses. Two-component regulatory systems (TCR systems) are the most ubiquitous signal transduction systems which regulate many genes required for virulence and survival of bacteria. In this study, I analyzed different TCR systems in two clinically-relevant Gram-negative bacteria, i.e., oral pathogen Porphyromonas gingivalis and enterobacterial Escherichia coli. P. gingivalis is a major causative agent of periodontal disease as well as systemic illnesses, like cardiovascular disease. A microarray study found that the putative PorY-PorX TCR system controls the secretion and maturation of virulence factors, as well as loci involved in the PorSS secretion system, which secretes proteinases, i.e., gingipains, responsible for periodontal disease. Proteomic analysis (SILAC) was used to improve the microarray data, reverse-transcription PCR to verify the proteomic data, and primer extension assay to determine the promoter regions of specific PorX regulated loci. I was able to characterize multiple genetic loci regulated by this TCR system, many of which play an essential role in hemagglutination and host-cell adhesion, and likely contribute to virulence in this bacterium. Enteric Gram-negative bacteria must withstand many host defenses such as digestive enzymes, low pH, and antimicrobial peptides (AMPs). The CpxR-CpxA TCR system of E. coli has been extensively characterized and shown to be required for protection against AMPs. Most recently, this TCR system has been shown to up-regulate the rfe-rff operon which encodes genes involved in the production of enterobacterial common antigen (ECA), and confers protection against a variety of AMPs. In this study, I utilized primer extension and DNase I footprinting to determine how CpxR regulates the ECA operon. My findings suggest that CpxR modulates transcription by directly binding to the rfe promoter. Multiple genetic and biochemical approaches were used to demonstrate that specific TCR systems contribute to regulation of virulence factors and resistance to host defenses in P. gingivalis and E. coli, respectively. Understanding these genetic circuits provides insight into strategies for pathogenesis and resistance to host defenses in Gram negative bacterial pathogens. Finally, these data provide compelling potential molecular targets for therapeutics to treat P. gingivalis and E. coli infections.
ContributorsLeonetti, Cori (Author) / Shi, Yixin (Thesis advisor) / Stout, Valerie (Committee member) / Nickerson, Cheryl (Committee member) / Sandrin, Todd (Committee member) / Arizona State University (Publisher)
Created2013
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Description
In the Rare-earth-Tri-telluride family, (RTe3s) [R=La, Ce, Nd, Sm, Gd, Tb, Dy, Er, Ho, Tm] the emergence of Charge Density Waves, (CDW) has been under investigation for a long time due to broadly tunable properties by either chemical substitution or pressure application. These quasi 2D Layered materials RTe3s undergo Fermi

In the Rare-earth-Tri-telluride family, (RTe3s) [R=La, Ce, Nd, Sm, Gd, Tb, Dy, Er, Ho, Tm] the emergence of Charge Density Waves, (CDW) has been under investigation for a long time due to broadly tunable properties by either chemical substitution or pressure application. These quasi 2D Layered materials RTe3s undergo Fermi Surface Nesting leading to CDW instability. CDWs are electronic instabilities found in low-dimensional materials with highly anisotropic electronic structures. Since the CDW is predominantly driven by Fermi-surface (FS) nesting, it is especially sensitive to pressure-induced changes in the electronic structure. The FS of RTe3s is a function of p-orbitals of Tellurium atoms, which are arranged in two adjacent planes in the crystal structure. Although the FS and electronic structure possess a nearly four-fold symmetry, RTe3s form an incommensurate CDW.This dissertation is structured as follows: Chapter 1 includes basic ideas of Quantum materials, followed by an introduction to CDW and RTe3s. In Chapter 2, there are fundamentals of crystal growth by Chemical Vapor Transport, including various precursors, transport agent, temperature gradient, and rate of the reaction. After the growth, the crystals were confirmed for lattice vibrations by Raman, for composition by Energy Dispersive Spectroscopy; crystal structure and orientation were confirmed by X-ray Diffraction; magnetic ordering was established by Vibrating sample measurement. Detailed CDW study was done on various RTe3s by Raman spectroscopy. The basic mechanism and instrumentations used in these characterizations are explained in Chapter 3. Chapter 4 includes experimental data for crystal growth and results of these characterizations for Parent RTe3s. Chapter 5 includes fundamental insights on Cationic alloying of RTe3s, along with one alloy system’s crystal growth and characterization. This work tries to explain the behavior of CDW by a Temperature-dependent Raman study of RTe3s established the CDW transition temperature accompanied by Phonon softening; Angle-resolved Raman data confirming the nearly four-fold symmetry; thickness-dependent Raman spectroscopy resulting in the conclusion that as thickness decreases CDW transition temperature increases. Also, CDW transition is analyzed as a function of alloying.
ContributorsAttarde, Yashika (Author) / Tongay, Sefaattin (Thesis advisor) / Botana, Antia (Committee member) / Alford, Terry (Committee member) / Arizona State University (Publisher)
Created2021
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Description
Doping is the cornerstone of Semiconductor technology, enabling the functionalities of modern digital electronics. Two-dimensional (2D) transition metal dichalcogenides (TMDCs) have tunable direct bandgaps, strong many-body interactions, and promising applications in future quantum information sciences, optoelectronic, spintronic, and valleytronic devices. However, their wafer-scale synthesis and precisely controllable doping are challenging.

Doping is the cornerstone of Semiconductor technology, enabling the functionalities of modern digital electronics. Two-dimensional (2D) transition metal dichalcogenides (TMDCs) have tunable direct bandgaps, strong many-body interactions, and promising applications in future quantum information sciences, optoelectronic, spintronic, and valleytronic devices. However, their wafer-scale synthesis and precisely controllable doping are challenging. Moreover, there is no fixed framework to identify the doping concentration, which impedes their process integration for future commercialization. This work utilizes the Neutron Transmutation Doping technique to control the doping uniformly and precisely in TMDCs. Rhenium and Tin dopants are introduced in Tungsten- and Indium-based Chalcogenides, respectively. Fine-tuning over 0.001% doping level is achieved. Precise analytical techniques such as Gamma spectroscopy and Secondary Ion Mass Spectrometry are used to quantify ultra-low doping levels ranging from 0.005-0.01% with minimal error. Dopants in 2D TMDCs often exhibit a broad stokes-shifted emission, with high linewidths, due to extrinsic effects such as substrate disorder and surface adsorbates. A well-defined bound exciton emission induced by Rhenium dopants in monolayer WSe2 and WS2 at liquid nitrogen temperatures is reported along with specific annealing regimes to minimize the defects induced in the Neutron Transmutation process. This work demonstrates a framework for Neutron Doping in 2D materials, which can be a scalable process for controlling doping and doping-induced effects in 2D materials.
ContributorsLakhavade, Sushant Sambhaji (Author) / Tongay, Sefaattin (Thesis advisor) / Alford, Terry (Committee member) / Yang, Sui (Committee member) / Arizona State University (Publisher)
Created2023
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Description
In the past decade, 2D materials especially transition metal dichalcogenides (TMDc), have been studied extensively for their remarkable optical and electrical properties arising from their reduced dimensionality. A new class of materials developed based on 2D TMDc that has gained great interest in recent years is Janus crystals. In contrast

In the past decade, 2D materials especially transition metal dichalcogenides (TMDc), have been studied extensively for their remarkable optical and electrical properties arising from their reduced dimensionality. A new class of materials developed based on 2D TMDc that has gained great interest in recent years is Janus crystals. In contrast to TMDc, Janus monolayer consists of two different chalcogen atomic layers between which the transition metal layer is sandwiched. This structural asymmetry causes strain buildup or a vertically oriented electric field to form within the monolayer. The presence of strain brings questions about the materials' synthesis approach, particularly when strain begins to accumulate and whether it causes defects within monolayers.The initial research demonstrated that Janus materials could be synthesized at high temperatures inside a chemical vapor deposition (CVD) furnace. Recently, a new method (selective epitaxy atomic replacement - SEAR) for plasma-based room temperature Janus crystal synthesis was proposed. In this method etching and replacing top layer chalcogen atoms of the TMDc monolayer happens with reactive hydrogen and sulfur radicals. Based on Raman and photoluminescence studies, the SEAR method produces high-quality Janus materials. Another method used to create Janus materials was the pulsed laser deposition (PLD) technique, which utilizes the interaction of sulfur/selenium plume with monolayer to replace the top chalcogen atomic layer in a single step. The goal of this analysis is to characterize microscale defects that appear in 2D Janus materials after they are synthesized using SEAR and PLD techniques. Various microscopic techniques were used for this purpose, as well as to understand the mechanism of defect formation. The main mechanism of defect formation was proposed to be strain release phenomena. Furthermore, different chalcogen atom positions within the monolayer result in different types of defects, such as the appearance of cracks or wrinkles across monolayers. In addition to investigating sample topography, Kelvin probe force microscopy (KPFM) was used to examine its electrical properties to see if the formation of defects impacts work function. Further study directions have been suggested for identifying and characterizing defects and their formation mechanism in the Janus crystals to understand their fundamental properties.
ContributorsSinha, Shantanu (Author) / Tongay, Sefaattin (Thesis advisor) / Alford, Terry (Committee member) / Yang, Sui (Committee member) / Arizona State University (Publisher)
Created2022
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Description
Many important technologies, including electronics, computing, communications, optoelectronics, and sensing, are built on semiconductors. The band gap is a crucial factor in determining the electrical and optical properties of semiconductors. Beyond graphene, newly found two-dimensional (2D) materials have semiconducting bandgaps that range from the ultraviolet in hexagonal boron nitride to

Many important technologies, including electronics, computing, communications, optoelectronics, and sensing, are built on semiconductors. The band gap is a crucial factor in determining the electrical and optical properties of semiconductors. Beyond graphene, newly found two-dimensional (2D) materials have semiconducting bandgaps that range from the ultraviolet in hexagonal boron nitride to the terahertz and mid-infrared in bilayer graphene and black phosphorus, visible in transition metal dichalcogenides (TMDs). These 2D materials were shown to have highly controllable bandgaps which can be controlled by alloying. Only a small number of TMDs and monochalcogenides have been alloyed, though, because alloying compromised the material's Van der Waals (Vdw) property and the stability of the host crystal lattice phase. Phase transition in 2D materials is an interesting phenomenon where work has been done only on few TMDs namely MoTe2, MoS2, TaS2 etc.In order to change the band gaps and move them towards the UV (ultraviolet) and IR (infrared) regions, this work has developed new 2D alloys in InSe by alloying them with S and Te at 10% increasing concentrations. As the concentration of the chalcogens (S and Te) increased past a certain point, a structural phase transition in the alloys was observed. However, pinpointing the exact concentration for phase change and inducing phase change using external stimuli will be a thing of the future. The resulting changes in the crystal structure and band gap were characterized using some basic characterization techniques like scanning electron microscopy (SEM), X-ray Diffraction (XRD), Raman and photoluminescence spectroscopy.
ContributorsYarra, Anvesh Sai (Author) / Tongay, Sefaattin (Thesis advisor) / Yang, Sui (Committee member) / Alford, Terry (Committee member) / Arizona State University (Publisher)
Created2022
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Description
Metal-Oxide-Semiconductor (MOS) is essential to modern VLSI devices. In the past decades, a wealth of literature has been created to understand the impact of the radiation-induced charges on the devices, i.e., the creation of electron-hole pairs in the oxide layer which is the most sensitive part of MOS structure to

Metal-Oxide-Semiconductor (MOS) is essential to modern VLSI devices. In the past decades, a wealth of literature has been created to understand the impact of the radiation-induced charges on the devices, i.e., the creation of electron-hole pairs in the oxide layer which is the most sensitive part of MOS structure to the radiation effect. In this work, both MOS and MNOS devices were fabricated at ASU NanoFab to study the total ionizing dose effect using capacitance-voltage (C-V) electrical characterization by observing the direction and amounts of the shift in C-V curves and electron holography observation to directly image the charge buildup at the irradiated oxide film of the oxide-only MOS device.C-V measurements revealed the C-V curves shifted to the left after irradiation (with a positive bias applied) because of the net positive charges trapped at the oxide layer for the oxide-only sample. On the other hand, for nitride/oxide samples with positive biased during irradiation, the C-V curve shifted to the right due to the net negative charges trapped at the oxide layer. It was also observed that the C-V curve has less shift in voltage for MNOS than MOS devices after irradiation due to the less charge buildup after irradiation. Off-axis electron holography was performed to map the charge distribution across the MOSCAP sample. Compared with both pre-and post-irradiated samples, a larger potential drop at the Si/SiO2 was noticed in post-irradiation samples, which indicates the presence of greater amounts of positive charges that buildup the Si/SiO2 interface after the TID exposure. TCAD modeling was used to extract the density of charges accumulated near the SiO2/Si and SiO2/ Metal interface by matching the simulation results to the potential data from holography. The increase of near-interface positive charges in post-irradiated samples is consistent with the C-V results.
ContributorsChang, Ching Tao (Author) / Barnaby, Hugh (Thesis advisor) / Holbert, Keith (Committee member) / Tongay, Sefaattin (Committee member) / Arizona State University (Publisher)
Created2023
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Description
Vanadium-dioxide-based devices show great switchability in their optical properties due to its dramatic thermochromic phase transition from insulator to metal, but generally have concerns due to its relatively high transition temperature at 68 °C. Doping the vanadium dioxide with tungsten has been shown to reduce its transition temperature at the

Vanadium-dioxide-based devices show great switchability in their optical properties due to its dramatic thermochromic phase transition from insulator to metal, but generally have concerns due to its relatively high transition temperature at 68 °C. Doping the vanadium dioxide with tungsten has been shown to reduce its transition temperature at the cost lower optical property differences between its insulating and metallic phases. A recipe is developed through parametric experimentation to fabricate tungsten-doped vanadium dioxide consisting of a novel dual target co-sputtering deposition, a furnace oxidation process, and a post-oxidation annealing process. The transmittance spectra of the resulting films are measured via Fourier-transform infrared spectroscopy at different temperatures to confirm the lowered transition temperature and analyze their thermal-optical hysteresis behavior through the transition temperature range. Afterwards, the optical properties of undoped sputtered vanadium films are modeled and effective medium theory is used to explain the effect of tungsten dopants on the observed transmittance decrease of doped vanadium dioxide. The optical modeling is used to predict the performance of tungsten-doped vanadium dioxide devices, in particular a Fabry-Perot infrared emitter and a nanophotonic infrared transmission filter. Both devices show great promise in their optical properties despite a slight performance decrease from the tungsten doping. These results serve to illustrate the excellent performance of the co-sputtered tungsten-doped vanadium dioxide films.
ContributorsChao, Jeremy (Author) / Wang, Liping (Thesis advisor) / Wang, Robert (Committee member) / Tongay, Sefaattin (Committee member) / Arizona State University (Publisher)
Created2022
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Description
Salmonella enterica serovar Typhimurium (S. Typhimurium) is a Gram-negative enteric pathogen that causes self-limiting gastroenteritis in healthy individuals and can cause systemic infections in those who are immunocompromised. During its natural lifecycle, S. Typhimurium encounters a wide variety of stresses it must sense and respond to in a dynamic and

Salmonella enterica serovar Typhimurium (S. Typhimurium) is a Gram-negative enteric pathogen that causes self-limiting gastroenteritis in healthy individuals and can cause systemic infections in those who are immunocompromised. During its natural lifecycle, S. Typhimurium encounters a wide variety of stresses it must sense and respond to in a dynamic and coordinated fashion to induce resistance and ensure survival. Salmonella is subjected to a series of stresses that include temperature shifts, pH variability, detergent-like bile salts, oxidative environments and changes in fluid shear levels. Previously, our lab showed that cultures of S. Typhimurium grown under physiological low fluid shear (LFS) conditions similar to those encountered in the intestinal tract during infection uniquely regulates the virulence, gene expression and pathogenesis-related stress responses of this pathogen during log phase. Interestingly, the log phase Salmonella mechanosensitive responses to LFS were independent of the master stress response sigma factor, RpoS, departing from our conventional understanding of RpoS regulation. Since RpoS is a growth phase dependent regulator with increased stability in stationary phase, the current study investigated the role of RpoS in mediating pathogenesis-related stress responses in stationary phase S. Typhimurium grown under LFS and control conditions. Specifically, stationary phase responses to acid, thermal, bile and oxidative stress were assayed. To our knowledge the results from the current study demonstrate the first report that the mechanical force of LFS globally alters the S. Typhimurium χ3339 stationary phase stress response independently of RpoS to acid and bile stressors but dependently on RpoS to oxidative and thermal stress. This indicates that fluid shear-dependent differences in acid and bile stress responses are regulated by alternative pathway(s) in S. Typhimurium, were the oxidative and thermal stress responses are regulated through RpoS in LFS conditions. Results from this study further highlight how bacterial mechanosensation may be important in promoting niche recognition and adaptation in the mammalian host during infection, and may lead to characterization of previously unidentified pathogenesis strategies.
ContributorsCrenshaw, Keith (Author) / Nickerson, Cheryl A. (Thesis advisor) / Barrila, Jennifer (Thesis advisor) / Ott, C. (Committee member) / Stout, Valerie (Committee member) / Arizona State University (Publisher)
Created2016
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Description
The emergence of invasive non-Typhoidal Salmonella (iNTS) infections belonging to sequence type (ST) 313 are associated with severe bacteremia and high mortality in sub-Saharan Africa. Distinct features of ST313 strains include resistance to multiple antibiotics, extensive genomic degradation, and atypical clinical diagnosis including bloodstream infections, respiratory symptoms, and fever. Herein,

The emergence of invasive non-Typhoidal Salmonella (iNTS) infections belonging to sequence type (ST) 313 are associated with severe bacteremia and high mortality in sub-Saharan Africa. Distinct features of ST313 strains include resistance to multiple antibiotics, extensive genomic degradation, and atypical clinical diagnosis including bloodstream infections, respiratory symptoms, and fever. Herein, I report the use of dynamic bioreactor technology to profile the impact of physiological fluid shear levels on the pathogenesis-related responses of ST313 pathovar, 5579. I show that culture of 5579 under these conditions induces profoundly different pathogenesis-related phenotypes than those normally observed when cultures are grown conventionally. Surprisingly, in response to physiological fluid shear, 5579 exhibited positive swimming motility, which was unexpected, since this strain was initially thought to be non-motile. Moreover, fluid shear altered the resistance of 5579 to acid, oxidative and bile stress, as well as its ability to colonize human colonic epithelial cells. This work leverages from and advances studies over the past 16 years in the Nickerson lab, which are at the forefront of bacterial mechanosensation and further demonstrates that bacterial pathogens are “hardwired” to respond to the force of fluid shear in ways that are not observed during conventional culture, and stresses the importance of mimicking the dynamic physical force microenvironment when studying host-pathogen interactions. The results from this study lay the foundation for future work to determine the underlying mechanisms operative in 5579 that are responsible for these phenotypic observations.
ContributorsCastro, Christian (Author) / Nickerson, Cheryl A. (Thesis advisor) / Ott, C. Mark (Committee member) / Roland, Kenneth (Committee member) / Barrila, Jennifer (Committee member) / Arizona State University (Publisher)
Created2016
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Description
This thesis presents systematic studies on angle dependent Raman and Photoluminescence (PL) of a new class of layered materials, Transition Metal Trichalcogenides (TMTCs), which are made up of layers possessing anisotropic structure within the van-der-Waals plane. The crystal structure of individual layer of MX3 compounds consists of aligned nanowire like

This thesis presents systematic studies on angle dependent Raman and Photoluminescence (PL) of a new class of layered materials, Transition Metal Trichalcogenides (TMTCs), which are made up of layers possessing anisotropic structure within the van-der-Waals plane. The crystal structure of individual layer of MX3 compounds consists of aligned nanowire like 1D chains running along the b-axis direction. The work focuses on the growth of two members of this family - ZrS3 and TiS3 - through Chemical Vapor Transport Method (CVT), with consequent angle dependent Raman and PL studies which highlight their in-plane optically anisotropic properties. Results highlight that the optical properties of few-layer flakes are highly anisotropic as evidenced by large PL intensity variation with polarization direction (in ZrS3) and an intense variation in Raman intensity with variation in polarization direction (in both ZrS3 and TiS3).

Results suggest that light is efficiently absorbed when E-field of the polarized incident excitation laser is polarized along the chain (b-axis). It is greatly attenuated and absorption is reduced when field is polarized perpendicular to the length of 1D-like chains, as wavelength of the exciting light is much longer than the width of each 1D chain. Observed PL variation with respect to the azimuthal flake angle is similar to what has been previously observed in 1D materials like nanowires. However, in TMTCs, since the 1D chains interact with each other, it gives rise to a unique linear dichroism response that falls between 2D and 1D like behavior. These results not only mark the very first demonstration of high PL polarization anisotropy in 2D systems, but also provide a novel insight into how interaction between adjacent 1D-like chains and the 2D nature of each layer influences the overall optical anisotropy of Quasi-1D materials. The presented results are anticipated to have impact in technologies involving polarized detection, near-field imaging, communication systems, and bio-applications relying on the generation and detection of polarized light.
ContributorsPant, Anupum (Author) / Tongay, Sefaattin (Thesis advisor) / Alford, Terry Lynn (Committee member) / He, Ximin (Committee member) / Arizona State University (Publisher)
Created2016