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Synthesis Of Molybdenum Containing Thin Films Using Organic Reducing Agents And Synthesis Of Magnesium Silyl Intermediate Complexes For Use In Atomic Layer Deposition, Michael David Overbeek

Wayne State University Dissertations

Thin films of a variety of materials have shown great potential in the fields of microelectronics, catalysis, and energy applications. Vapor deposition methods, including PVD and CVD, have been traditionally used as the primary method to deposit these thin films. However, these methods do not provide the necessary thickness uniformity and conformality needed for future uses of these thin films as they shrink to smaller dimensions. ALD provides a high degree of uniformity and conformality due to the intrinsic nature of the self-limited reaction mechanism of an ALD process.

The research herein focuses on two metals that have untapped potential …

The Development Of Fundamental Insights Into The Electronic Behaviors Of Next-Generation Materials, Sydney Lavan

Wayne State University Dissertations

We develop the fundamental mechanistic understanding of the microscopic behavior of three next generation materials: antiferroelectrics, hybrid perovskites and metal organic frameworks. These materials have the potential to be used in energy and light related applications which could provide a solution for the energy efficiency challenges we face in todays society. Ideally we need to begin to bridge the gap of developing candidate materials that possess high power density and high energy density. The first step in bridging this gap is understanding how the material influ- ences its structure and thus the properties and performance. We leverage vibrational spectroscopy and …

Lepton Flavor Violation And Effective Field Theories, Renae Conlin

Wayne State University Dissertations

The Standard Model is believed to be a low energy effective theory of some completetheory at higher energies. This is already evidenced in the observation of neutrino oscillations. Standard Model processes conserve the lepton flavor quantum numbers. Adding massive neutrinos to the Standard Model, the branching ratios of lepton flavor violating processes are found to be incredibly small. For example, a process μ → eγ has a branching ratio order ∼ 10^−54. These tiny branching ratios of lepton flavor violating processes indicate that they are especially clean areas to look for beyond the Standard Model physics. Any observed flavor violation …

Segmentation Of Intracranial Structures From Noncontrast Ct Images With Deep Learning, Evan Porter

Wayne State University Dissertations

Presented in this work is an investigation of the application of artificially intelligent algorithms, namely deep learning, to generate segmentations for the application in functional avoidance radiotherapy treatment planning. Specific applications of deep learning for functional avoidance include generating hippocampus segmentations from computed tomography (CT) images and generating synthetic pulmonary perfusion images from four-dimensional CT (4DCT).A single institution dataset of 390 patients treated with Gamma Knife stereotactic radiosurgery was created. From these patients, the hippocampus was manually segmented on the high-resolution MR image and used for the development of the data processing methodology and model testing. It was determined that …

Development Of New Photochemical Tools For Applications In Cancer Research And Enzymatic Signaling, Nicholas Paul Toupin

Wayne State University Dissertations

Photochemical tools empower researchers to act with precision and control over the cellular environment through production of reactive oxygen species (ROS), targeted drug delivery, and modulation of enzymatic activity. These molecular tools use light as a readily available, biorthogonal reagent for initiating advantageous light-activated reactions. Using light in this way allows researchers to affect the cellular environment in specific ways with high spatio-temporal control. This dissertation focuses on expanding the applications of, mostly Ru(II)-based, photoactivated chemicals. Complexes of this type are able to act as photosensitizers in photodynamic therapy (PDT), as photocages (PCT), or as dual-action compounds capable of both …

Correlations And Dynamic Fluctuations In High Energy Collisions, Zoulfekar Mazloum

Wayne State University Dissertations

Is thermalization necessary for hydrodynamic flow in nuclear collisions? The discovery of flow-like azimuthal correlations in pA and high-multiplicity pp collisions raises profound questions about the onset of collective flow and its relation to hydrodynamics. We seek independent experimental information on the degree of thermalization in order to identify those hydrodynamic collision systems in which flow is sensitive to equilibrium QCD properties. We aim to develop a protocol for identifying the degree of thermalization using a combination of momentum and multiplicity correlation. To study the effect ofthermalization on these correlations, we use Boltzmann equation in the relaxation time approximation with …

Photophysics Of Metalloporphyrins Strongly Coupled To Cavity Photons, Aleksandr Avramenko

Wayne State University Dissertations

This dissertation will discuss the photophysics of metalloporphyrins, mainly CuTPP, ZnTPP, and H2TPP under strong light-matter coupling conditions. Strong light-matter coupling was achieved by embedding the previously mentioned chromophores into a spun coated PMMA polymer coating which is then incorporated as a spacer layer in a FabryPérot nano-cavity. The cavity thickness is chosen so that the cavity photon is of similar energy as the B, or Soret transition (2nd excited state) of the porphyrin molecule. The exchange of energy between the cavity photon and the molecular mode leads to the formation of polariton states.

Increasing the concentration of the molecules …

Kinase-Catalyzed Labeling To Identify Kinase-Substrate Pairs Using Γ-Phosphate Modified Atp Analogs, Rachel Beltman

Wayne State University Dissertations

Post-translational modifications (PTMs) are responsible for a variety of cellular processes. One such PTM is protein phosphorylation, which is catalyzed by kinases. Kinase enzymes play important roles in cellular signaling pathways, but dysregulation of kinase-mediated events results in the formation of diseases, which make kinases favorable drug targets. To uncover the role kinases play in the development of diseases, kinase-mediated cellular events need to be better understood. The current gap in the field is the lack of tools available to identify the kinase that is responsible for specific phosphorylation events within the cell. To improve the gap in the field, …

Study Of Zyomogen Granule Movement Along Actin Filaments Using A Single Beam Optical Trap, Justin James Raupp

Wayne State University Dissertations

Zymogen granules are enzymatic vesicles in the pancreas. The surface of these zymogen granules (ZGs) has several different kinds of myosin molecules, such as myosin 1c, 6, 5c, and 7b. These molecular motors may contribute to ZG transportation in cells. To understand the molecular motors involved in the vesicle trafficking, we observed the in vitro motility of purified ZGs from rat pancreas and examined the stepping behavior and force that is generated using a single beam optical trap. To be involved in trafficking, molecular motors have certain characteristics, a high duty ratio and the ability to move continuously along actin …

A C0 Finite Element Method For The Biharmonic Problem In A Polygonal Domain, Charuka Dilhara Wickramasinghe

Wayne State University Dissertations

This dissertation studies the biharmonic equation with Dirichlet boundary conditions in a polygonal domain. The biharmonic problem appears in various real-world applications, for example in plate problems, human face recognition, radar imaging, and hydrodynamics problems. There are three classical approaches to discretizing the biharmonic equation in the literature: conforming finite element methods, nonconforming finite element methods, and mixed finite element methods. We propose a mixed finite element method that effectively decouples the fourth-order problem into a system of one steady-state Stokes equation and one Poisson equation. As a generalization to the above-decoupled formulation, we propose another decoupled formulation using a …

Assembly Of Quantum Dots Into Porous Architectures: Methods, Mechanisms, And Applications, Karunamuni Lakmini Samantha Silva

Wayne State University Dissertations

ABSTRACT ASSEMBLY OF QUANTUM DOTS INTO POROUS ARCHITECTURES: METHODS, MECHANISMS, AND APPLICATIONS by KARUNAMUNI LAKMINI SAMANTHA SILVA May 2022 Advisor: Prof. Stephanie L. Brock Major: Chemistry Degree: Doctor of Philosophy The dissertation research is focused on achieving two main goals: (1) identifying the chemical parameters that govern the oxidative assembly method of semiconductor metal chalcogenide nanocrystals (NCs) to tune the properties of resultant gel structures of multicomponent systems, and (2) developing new assembly techniques to improve properties associated with their quantum-confined structures. NC assembly plays a key role in determining the performance of solid-state devices and the oxidative assembly method …

Development Of Terpyridine-Based Metallosurfactants For Directional Electron Tunneling, Samudra Subashini Amunugama

Wayne State University Dissertations

The molecular electronics field is a multidisciplinary area that addresses the utilization of molecules as the basic unit of electronic components. Depending on the characteristics of the molecules, they can function as transistors, wires, switches, and memory cells. This field has attracted significant interest from the scientific community due to the increasing number of issues associated with the miniaturization process of microelectronic devices and the desirability of using molecules in electronic circuits. The research work discussed in this dissertation thesis is focused on the design and development of terpyridine-based metallosurfactant as prospective candidates for molecular electronics. Since rectifiers are pivotal …

Development Of Carbohydrate-Based Antibiotics And Metabolic Chemical Reporters, Courtney Kondor

Wayne State University Dissertations

CHAPTER 1: Multidrug-resistant bacteria is a threat to public health and there is a need for the development of new antibiotics to fight bacterial resistance. Aminoglycoside antibiotics are attractive to researchers due to their lack of known drug related allergies, low cost, and broad spectrum of activity; however, they can cause nephrotoxicity and ototoxicity in patients. We modified the 2-deoxystreptamine ring of paromomycin to make the drug more flexible and potentially more selective for the bacterial ribosomal A-site to circumvent off-target effects that cause ototoxicity. However, we found that our compound, paromomexin, was significantly less active than paromomycin in all …

Synthetic, Mechanistic, And Structural Insights Into Defect Mediated Broadband Photoluminescence In Low Dimensional Hybrid Perovskites, Adedayo M. Sanni

Wayne State University Dissertations

The research projects in this dissertation focused on understanding the light emission and structure of hybrid organic inorganic hybrid perovskites. There remains a need to develop novel synthetic approaches to synthesize self-assembled hybrid organic-inorganic nanostructures to enable solution processed lighting technologies. Bulk of the approachescurrently employed in making light emitting diodes (LEDs) for lighting applications involves complex fabrication techniques. Hence, we investigated the light emission properties of 2D hybrid organic inorganic lighting materials as potential materials for lighting applications. In Chapter 2, we employed a solvothermal approach to synthesize so called self-assembled quantum wells (SAQWs) that emit narrow light centered …

Lanthanide Coordination Chemistry In Rare-Earth Element Extraction And Photocatalysis, Jessica Hovey

Wayne State University Dissertations

This thesis outlines projects pertaining to the extraction, enrichment, and use of rare-earth elements in the trivalent and divalent states through the modification of coordination chemistry. Modulating the coordination environment can impact the selectivity of rare-earth elements in solid-liquid enrichment through the adjustment of donor atoms, denticity and pKa values as detailed in Chapter 1. Changes in coordination environment, such as to the identity of donor atoms, can lead to major differences in properties such as luminescence. The studies reported in this thesis contribute to the body of knowledge surrounding the use of coordination chemistry for both the solid–liquid extraction …

Chemical Proteomic Identification And Functional Studies Of Cardiac Protein Glutathionylation, Maheeshi Yapa Abeywardana

Wayne State University Dissertations

Elevated intracellular levels of reactive oxygen species (ROS) are associated with induction of oxidative stress. Increased levels of ROS participate in development of cardiovascular diseases by modifying proteins reversibly or irreversibly. Especially, the cysteine residues can undergo oxidative post-translational modifications such as glutathionylation. Glutathionylation is an important regulatory reversible thiol oxidation. Identification and quantification of glutathionylated proteins is important for the understanding of the molecular mechanisms behind initiation and progression of many diseases. Our lab previously developed a click chemistry-based method to detect and identify glutathionylation in cells by synthesizing clickable-glutathione.We established a mass spectrometry-based strategy coupled with clickable glutathione …

Understanding The Effects Of Ligand Environment On Important Properties Of Redox-Active Europium Using Computational Chemistry And T1-Weighted Magnetic Resonance Imaging, Brooke Anne Corbin

Wayne State University Dissertations

This thesis is a collection of seven chapters that describes a combination of literature research and experimental analyses into the study of inorganic complexes, with an emphasis on the photophysics and coordination of redox-active europium. The first chapter summarizes the key features of each chapter. The second and third chapters are detailed overviews, including historical context, current studies, and future goals of imaging science, with an emphasis on inorganic complexes. The fourth chapter describes the design of a screening procedure to study new ligand environments for redox-active europium using magnetic resonance imaging and a proof-of-concept experiment. The fifth chapter is …

Extending Plasma Proteome Coverage To Enable Biomarker Discovery, Jordan Bruce Burton

Wayne State University Dissertations

Two features make plasma a valued source of health information: First, plasma contains secreted proteins from all tissues in the body and can, therefore, provide information about the health status of all tissues. Second, plasma is available in large quantity using a minimally invasive procedure that is well tolerated. The status of plasma as a valued source of health information is matched by the difficulty in extracting proteome information from the samples. Using state of the art instrumentation a standard analysis of plasma yields quantitative information on approximately 300 proteins. Extreme fractionation strategies coupled with increased mass spectrometry time extends …

Securing Big Data Scientific Workflows & Gpgpu Computation In The Commodity Cloud With Hardware-Assisted Trusted Execution Environments, Saeid Mofrad

Wayne State University Dissertations

Nowadays, big data analytics are essential tools for helping businesses, healthcare providers, and decision-makers in society, in making important and strategic choices that benefit their business, patients, and people. Processing big data requires massive amounts of computing and storage resources due to the nature of big data characteristics. Cloud providers with their low-cost, elastic, and enormous amounts of hardware and software resources are a suitable platform for deploying big data analytics systems. Also, the increasing demand for GPU accelerator instances from big data and machine learning applications encourages cloud providers to invest in GPU servers to enable the provisioning of …

Parallel Algorithms For Steiner Forest, Laleh Ghalami

Wayne State University Dissertations

The Steiner Forest Problem is one of the fundamental combinatorial optimization problemsin operations research and computer science. Its applications range from network design to computational biology. Given an undirected graph with non-negative weights for edges and a set of pairs of vertices called terminals, the Steiner Forest Problem is to find the minimum cost subgraph that connects each of the terminal pairs together. The Steiner Forest Problem is APX-hard and NP-hard to approximate within 96/95. Several heuristic and approximation algorithms, with different approximation guarantees, have been proposed for the Steiner Forest Problem. Despite the several research in designing sequential and …

Deep Learning As Native Scientific Workflows In The Modern Swfms - Dataview, Junwen Liu

Wayne State University Dissertations

Scientific workflow has become a common practice for scientists to effectively formalize and structure complex scientific processes, which in turn has accelerated scientific discoveries in numerous research fields. With the recent thriving of deep learning in broad scientific projects, there is a rising need for deep learning support in scientific workflow infrastructures SWFMSs. However, current GPU-enabled deep learning frameworks are developed separately, not suitable for direct exploitation in SWFMSs, which forces scientists to handle deep learning outside of SWFMSs and then integrate in workflows in an ad-hoc manner. What workflow users pressingly need today is a user-friendly and well-integrated SWFMS …

Jet Substructure Measurements In Proton-Proton And Proton-Gold Collisions, Isaac Arthur Mooney

Wayne State University Dissertations

Observing a modification of high-energy probes in the hot nuclear environment created by ultrarelativistic heavy-ion collisions is critical for understanding the microscopic structure of the QCD medium. However, before a modification can be observed, the probes must be calibrated. For this reason, measurements of jet observables in vacuum (pp collisions) and in the presence of cold nuclear matter (pAu collisions) are presented, which will allow for future comparison of jet substructure measurements in AuAu to these baseline measurements. \parData from the STAR detector on the Relativistic Heavy Ion Collider at Brookhaven National Laboratory are used for both analyses. The pp …

Synthesis And Investigation Of Properties In Ternary Transition Metal Phosphide Nanomaterials For Electrochemical Water Splitting, Tharanga Nisansala Batugedara

Wayne State University Dissertations

Nanoscale transition metal phosphides are emerging as efficient catalysts for hydrogen production via electrochemical water splitting. Although monometallic phases have been extensively studied, enhanced catalytic activities and stabilities can be gained by the synergism of two metals in bimetallic ternary transition metal phosphides. In this dissertation, we report (1) the effect of the counter electrode and electrolyte on stabilities of Co2−xRhxP nanoparticles for water reduction (hydrogen evolution reaction, HER), (2) novel synthetic protocol development and electrocatalytic water splitting activity and stability study on Ni2-xRhxP nanoparticles, and (3) a preliminary investigation employing cation exchange methods to synthesize Cu-M-P (M= Fe, Co, …

Non-Perturbative Processes In Standard Model \& New Physics: From Standard Calculations To Machine Learning, Cody Michael Grant

Wayne State University Dissertations

I calculated non-perturbative processes to study the Standard Model and probe areas of new physics. I found that invisible decays of heavy mesons are not dominated by the leading order contribution in the Standard Model. I argue that this affects neutrino mass constraints and avenues for discovering new physics, such as dark photons. In addition to this, I used a novel approach to approximate a semileptonic form factor with an artificial neural network (ANN). Comparing the results from the ANN to common phenomenological parameterizations, and using it to set a lower bound constraint on the CKM matrix element, $V_{cd}$. Finally, …

Adversarial Machine Learning For Advanced Medical Imaging Systems, Xin Li

Wayne State University Dissertations

Although deep neural networks (DNNs) have achieved significant advancement in various challenging tasks of computer vision, they are also known to be vulnerable to so-called adversarial attacks. With only imperceptibly small perturbations added to a clean image, adversarial samples can drastically change models’ prediction, resulting in a significant drop in DNN’s performance. This phenomenon poses a serious threat to security-critical applications of DNNs, such as medical imaging, autonomous driving, and surveillance systems. In this dissertation, we present adversarial machine learning approaches for natural image classification and advanced medical imaging systems.

We start by describing our advanced medical imaging systems to …

Optical Signal Processing With Discrete-Space Metamaterials, Mohammad Moein Moeini

Wayne State University Dissertations

As digital circuits are approaching the limits of Moore’s law, a great deal of efforthas been directed to alternative computing approaches. Among them, the old concept of optical signal processing (OSP) has attracted attention, revisited in the light of metamaterials and nano-photonics. This approach has been successful in realizing basic mathematical operations, such as derivatives and integrals, but it is difficult to be applied to more complex ones. Inspired by digital filters, we propose a radically new OSP approach, able to realize arbitrary mathematical operations over a nano-photonic platform. We demonstrate this concept for the case of spatial differentiation, image …

Electrochemical Gelation Of Metal Chalcogenide Quantum Dots, Chathuranga Chinthana Hewa Rahinduwage

Wayne State University Dissertations

Quantum dots (QDs) are attractive because of their unique size-dependent optical and electronic properties and high surface area. They are tested in research for diverse applications, including energy conversion, catalysis, and sensing. Assembling QDs into functional solid-state devices while preserving their attractive properties is a challenge. Methods currently under the research are not effective in directly fabricating QDs onto devices, making large area assemblies, maintaining the high surface area by forming 3D porous structures, and conducting electricity for applications such as sensing. QD gels are an example of QD assemblies that consist of a 3D porous interconnected QD network. They …

Study Of The Decay B^± → K^0_S Π^± Π^0 At The Belle Experiment, Suravinda Janaka Kumara Kospalage

Wayne State University Dissertations

Belle is a particle physics experiment based at the KEK laboratory in Tsukuba Japanwhich ran from 1999 to 2010 and collected 1ab−1 of data. The Belle experiment is focused on studying the properties of particles called B mesons which are produced by accelerating and colliding electron and positron beams. These B mesons show the biggest differences between the properties of matter and anti-matter of any known particles. One of the main goals of the Belle experiments is to understand the differences between matter and anti-matter, specifically violations of charge-parity symmetry (CP violation) and how anti-matter vanished and we come to …

Integral Representations Of Sl_2(Z/Nz), Yatin Dinesh Patel

Wayne State University Dissertations

The aim of this work is to determine for which commutative rings integral representations of SL_2(Z/nZ) exist and to explicitly compute them. We start with R = Z/pZ and then consider Z=p^\lambda Z. A new approach will be used to do this based on the Weil representation. We then consider general finite rings Z/nZ by extending methods described in [26]. We make extensive use of group theory, linear representations of finite groups, ring theory, algebraic geometry, and number theory. From number theory we will employ results regarding modular forms, Legendre symbols, Hilbert symbols, and quadratic forms. We consider the works …

Phenanthroline-Catalyzed 1,2-Cis Glycosylation: Scope And Mechanism, Jiayi Li

Wayne State University Dissertations

Phenanthroline, a rigid and planar organic compound with two fused pyridine rings, has been used as a powerful ligand for metals and a binding agent for DNA/RNA. We recently discovered that phenanthroline could be used as a nucleophilic catalyst to access high yielding and diastereoselective α-1,2-cis glycosides through the coupling of hydroxyl acceptors with α-glycosyl bromide donors. The utility of the phenanthroline catalysis is expanded to sterically hindered hydroxyl nucleophiles and chemoselective coupling of an alkyl hydroxyl group in the presence of a free C1-hemiacetal functionality. In addition, the phenanthroline-based catalyst has a pronounced effect on site-selective couplings of triol …