Physical Sciences and Mathematics Commons^™

Computational Study Of Transition Metal Complexes For Solar Energy Conversion And Molecular Interaction With Strong Laser Fields, Xuetao Shi

Wayne State University Dissertations

There are two topics in this dissertation: ground state and excited state modeling of a few series of transition metal complexes that facilitate solar energy conversion, and Born-Oppenheimer Molecular Dynamics (BOMD) simulations of molecular cations interacting with intense mid-infrared laser light.

In Chapter 2 and 3, a few series of transition metal complexes that facilitate solar energy conversion are studied computationally. Metal-to-ligand charge-transfer (MLCT) excited states of several (ruthenium) (monodentate aromatic ligand, MDA) chromophore complexes are modeled by using time-dependent density function theory (TD-DFT). The calculated MLCT states correlate closely with the heretofore unknown emission properties that were observed experimentally. …

Data-Driven Modeling For Decision Support Systems And Treatment Management In Personalized Healthcare, Milad Zafar Nezhad

Wayne State University Dissertations

Massive amount of electronic medical records (EMRs) accumulating from patients and populations motivates clinicians and data scientists to collaborate for the advanced analytics to create knowledge that is essential to address the extensive personalized insights needed for patients, clinicians, providers, scientists, and health policy makers. Learning from large and complicated data is using extensively in marketing and commercial enterprises to generate personalized recommendations. Recently the medical research community focuses to take the benefits of big data analytic approaches and moves to personalized (precision) medicine. So, it is a significant period in healthcare and medicine for transferring to a new paradigm. …

Toward Better Keys For Lectin Locks: Glycoconjugates Versus Glycomimetics, Peng Wen

Wayne State University Dissertations

As one of the four major classes of macromolecule in living systems, the roles of carbohydrates as energy storage substances and structural components have long been recognized. However, the unique role of carbohydrates in cellular recognition processes has only been scrutinized since the 1960s, thanks to the progress in the research in both cell surface carbohydrates and carbohydrate-binding proteins (lectins). The advances in the research of such process demand the use of carbohydrates as basic tools. Therefore, the primary goal of glycochemistry has been to obtain complex carbohydrates and their analogs effectively. One common approach to the problem involves the …

Magnetic Moment And Susceptibility Quantification In Mri: Additional Frequency Shifts From Materials And Background Phase Removal Using A Reference Phantom, He Xie

Wayne State University Dissertations

The first part of this thesis was to utilize existing methods to remove the unwanted background phase from phantom studies. Magnetic moments of straws filled by three different materials (gadolinium, ferritin, and nanoparticles) with four different concentrations of each material were subsequently quantified at 10 different echo times, with straws perpendicular to the main magnetic field. As the radius of each straw was known, susceptibility was calculated from each measured magnetic moment. Results from different echo times agreed within uncertainties. In addition, near perfect linear relation between quantified susceptibility and concentration was obtained for each material. However, phase values inside …

Cation Clock Reactions For The Determination Of Relative Reaction Kinetics In Glycosylation Reactions, Philip Adero

Wayne State University Dissertations

This dissertation presents the development of cyclization reactions as clocks for the determination of the molecularity of glycosylation reactions in individual pyranoside systems and extends it to the arabinofuranoside systems. It also describes the development of selective hydrogenolytic cleavage of naphthylmethyl ethers in the presence of sulfides.

The first part of chapter one gives an overview of the significance of glycochemistry and the challenges involved. The second part describes some selected glycosylation methods and extends this to the general mechanistic studies of glycosylation. This is followed by the discussion of the general clock reactions in literature which initiates a further …

3d Momentum Imaging Spectroscopy Probing Of Strong-Field Molecular And Surface Dynamics, Lin Fan

Wayne State University Dissertations

Electron-ion coincidence measurements in combination with 3-dimensional (3D) momentum imaging can provide comprehensive 3D-momentum information to unravel multichannel photoionization/dissociation processes, and thus is an effective tool to investigate atomic/molecular dynamics. A camera-based 3D coincidence momentum imaging system and the velocity mapping imaging (VMI) based machine were introduced in Chapter 2. Studies of strong field dissociative single and double ionization of relatively large molecules camphor and 2-phenylethyl-N, N-dimethylamine (PENNA) were carried out and illustrated in Chapter 3. We demonstrated the main products of double ionization of PENNA were singlet diradicals. In Chapter 4, a novel angle resolved-photoemission spectroscopy based on VMI …

Design, Synthesis, And Reactivity Of Homo- And Heterobimetallic Complexes Bridged By A Xanthene Linker, Thilini Samangi Hollingsworth

Wayne State University Dissertations

Cooperative reactivity of bimettalics can be is observed in many different areas of chemistry and have been increasingly investigated because of the advantageous reactivity when compared to the corresponding mononuclear systems. The focus of my dissertation is on (1) investigation of the homobimetallic cooperativity in lactide polymerization catalysis; (2) investigation of the heterobimetallic cooperativity in the biomimetic studies of Mo-Cu carbon monoxide dehydrogenase (CODH) enzyme in order to make a functional model of its active site.

Three new main group bis(alkoxide) complexes Mg(OR)2(THF)2, Zn(Cl)(μ2-OR)2Li(THF) and In(OR)2(μ2-Cl)2Li(THF)2 featuring bulky alkoxide [OCtBu2Ph] were synthesized serve as metal alkoxide precursors for bimetallic lactide …

Design And Synthesis Of Oligo-(3,5-Dithio-Β-D-Glucopyranoside) As Β-(1→3)-Glucan Mimetics, Xiaoxiao Liao

Wayne State University Dissertations

This dissertation presents the design and synthesis of oligo-(3,5-dithio-β-D-glucopyranoside) as β-(1 → 3)-D-glucan mimetics. The synthesized dimeric, trimeric and tetrameric mimetics were tested for their binding affinities to Dectin-1 and CR3 and their abilities to activate phagocytosis and pinocytosis.

The first chapter gives an introduction of β-(1 → 3)-D-glucan. It gives an introduction about the structure and origin of β-(1 → 3)-D-glucan as well as the immunostimulating effect of natural β-(1 → 3)-D-glucan. The study of interaction between β-(1 → 3)-D-glucan and the receptors leads to a conclusion that the hydrophobicity of β-(1 → 3)-D-glucan is crucial to its immunostimulating …

Synthesis Of Open-Chain And Macrocyclic Xanthene-Bridged Bimetallic Cobalt, Nickel, And Copper Complexes For Cooperative Catalysis, Ryan Lance Hollingsworth

Wayne State University Dissertations

Within the numerous fields of inorganic chemistry, there is a growing interest to design dinucleating ligands for transition metals. This interest derives from the expansive list of bimetallic and polymetallic centers observed in nature that employ vital small molecules for catalysis, such as carbon dioxide, dinitrogen, and water. Many research groups have attempted to harness that structural and functional metal-metal cooperativity displayed by these enzymes, in hopes of enhancing transition metal catalysis. The overall focus of my dissertation is on utilizing late first-row transition metals, bound to either iminopyridine, bis(imino)pyridine, or bis(2-pyridinylmethyl)amine chelates, tethered by a xanthene linker towards bimetallic …

Characterization Of Protonated Modified Nucleosides And Amino Acid-Linked Cisplatin Analogues Using Tandem Mass Spectrometry Complemented By Theoreticical Approaches, Chenchen He

Wayne State University Dissertations

The chemical difference between DNA and RNA nucleosides is their 2′-hydrogen versus 2′-hydroxyl substituents. The 2′-O-methylation is common among natural posttranscriptional modifications of RNA. The structures and relative glycosidic bond stabilities of the protonated forms of the 2′-O-methylated nucleosides, 2′-O-methyladenosine (Adom), 2′-O-methylguanosine (Guom), 2′-O-methycytidine (Cydm), 2′-O-methyluridine (Urdm), and 5,2′-O-dimethyluridine (Thdm) are examined using two complementary tandem mass spectrometry approaches, infrared multiple photon dissociation (IRMPD) action spectroscopy and energy-resolved collision-induced dissociation (ER-CID). Theoretical calculations are also performed to predict the structures and relative stabilities of stable low-energy conformations of the protonated forms of the 2′-O-methylated nucleosides and their infrared spectra in …

Drug Delivery Strategies For The Treatment Of Advanced Lung Cancer And Various Lung Metastases, Elizabeth Bielski

Wayne State University Dissertations

Lung cancer remains the leading cause of cancer-related deaths in the United States. Secondary lung tumors metastasized from other cancer sites also remains highly prevalent, in which most metastatic tumors cannot be cured with existing therapies. Chemoresistance (multi drug resistance – MDR) that develops intrinsically or acquired is one of the key factors leading to fatality in these patients. MDR develops form a variety of resistance mechanisms that can occur consecutively or concurrently, therefore, making most current treatments unsuccessful. Current therapies have known to slow tumor growth, but rarely provide a cure. Immunotherapy has seen some promise, including the use …

Spectral–Timing Analysis Of Kilohertz Quasi–Periodic Oscillations In Neutron Star Low Mass X-Ray Binaries, Jon Troyer

Wayne State University Dissertations

Kilohertz quasi-periodic oscillations or kHz QPOs are X-ray intensity variations observed

in neutron star low-mass X-ray binary (LMXB) systems. In such systems, matter is transferred

from a secondary low-mass star to a neutron star via the process of accretion. kHz

QPOs occur on the timescale of the inner accretion flow and may carry signatures of the

physics of strong gravity (c2 ~GM/R) and possibly clues to constraining the neutron star

equation of state (EOS). No model to date has been able to illuminate the origin of kHz

QPOs. Spectral-timing is a set of analysis techniques useful in deriving information about …

Polarized Localization Microscopy (Plm) Detects Nanoscale Membrane Curvature And Induced Budding By Cholera Toxin Subunit B (Ctxb), Abir Kabbani

Wayne State University Dissertations

The curvature of biological membranes at the nanometer scale is critically important for vesicle trafficking, organelle morphology, and disease propagation. Many proteins and lipids interact with diverse curvature sensing and curvature generating mechanisms. Deciphering the molecular mechanisms of toxin-membrane interactions has been limited by the resolution and drawbacks of conventional experimental techniques. This study reveals the inherent membrane bending capability of cholera toxin subunit B (CTxB) through the development and implementation of Polarized Localization Microscopy (PLM). PLM is a pointillist optical imaging technique for the detection of nanoscale membrane curvature in correlation with single-molecule dynamics and molecular sorting.

PLM combines …

Tandem Mass Spectrometry And Computational Approaches To Elucidate Conformations And N-Glycosidic Bond Stabilities Of Dna And Rna Nucleosides And Mononucleotides, Yanlong Zhu

Wayne State University Dissertations

ABSTRACT

TANDEM MASS SPECTROMETRY AND COMPUTATIONAL APPROACHES TO ELUCIDATE CONFORMATIONS AND N-GLYCOSIDIC BOND STABILITIES OF DNA AND RNA NUCLEOSIDES AND MONONUCLEOTIDES

by

YANLONG ZHU

May 2018

Advisor: Dr. Mary T. Rodgers

Major: Analytical Chemistry

Degree: Doctor of Philosophy

The influence of noncovalent interactions with sodium cations on the conformations and energetics of ten DNA and RNA nucleosides as well as two adenine mononucleotides were elucidated via infrared multiple photon dissociation (IRMPD) action spectroscopy experiments and complementary electronic structure calculations. Energy-resolved collision-induced dissociation (ER-CID) experiments of protonated and metal cationized DNA and RNA nucleosides were performed using a Bruker amaZon ETD …

Design Of Ruthenium(Ii) Polypyridyl Complexes For Effectively Caging Nitriles And Aromatic Heterocycles, Ao Li

Wayne State University Dissertations

ABSTRACT

DESIGN OF RUTHENIUM(II) POLYPYRIDYL COMPLEXES FOR EFFECTIVELY CAGING NITRILES

AND AROMATIC HETEROCYCLES

by

AO LI

May 2018

Advisor: Dr. Jeremy Kodanko

Major: Chemistry

Degree: Doctor of Philosophy

Ru(II) polypyridyl complexes have been frequently employed in the caging and photorelease of biologically active compounds. Traditional photocaging groups derived from Ru(II) have been largely based on bi- or tridentate ancillary ligands, and those bearing ancillary ligands with high-denticities are yet to be developed. Exploring Ru(II) polypyridyl complexes possessing ancillary ligands with high-denticities provides insight into the photophysical and photochemical properties of ruthenium complexes, which creates novel prospects in the design of …

Sdes, Jumps And Estimates, Jose L. Menaldi

Mathematics Faculty Research Publications

Long Title: Stochastic Ordinary Differential Equations with Jumps: Theory and Estimates. Chapters: Stochastic Integrals - Initial Approach to SDEs - Estimates of SDEs - Other Formulations of SDEs - SDEs with Reflection - PDE Connections.

Functional Study Of Smyd2 Glutathionylation In Cardiomyocytes, Dhanushka Nalin Perera Munkanatta Godage

Wayne State University Dissertations

Reactive oxygen species (ROS) are important signaling molecules that contribute to the etiology of multiple muscle-related diseases, including cardiomyopathy and heart failure. There is emerging evidence that cellular stress can lead to destabilization of sarcomeres, the contractile unit of muscle. However, it is not completely understood how cellular stress or ROS induce structural destabilization of sarcomeres or myofibrils. Protein glutathionylation is one of the major protein cysteine oxidative modifications that play an important role in redox signaling and oxidative stress. In this report, we used a clickable glutathione approach in a cardiomyocyte cell line, and found that SET and MYND …

Switching Diffusion Systems With Past-Dependent Switching Having A Countable State Space, Hai Dang Nguyen

Wayne State University Dissertations

Emerging and existing applications in wireless communications, queueing networks, biological models, financial engineering, and social networks demand the

mathematical modeling and analysis of hybrid models in which continuous dynamics and discrete events coexist.

Assuming that the systems are in continuous times,

stemming from stochastic-differential-equation-based models and random discrete events,

switching diffusions come into being. In such systems, continuous states and discrete events

(discrete states)

coexist and interact.

A switching diffusion is a two-component process $(X(t),\alpha(t))$, a continuous component and a discrete component taking values in a discrete set (a set consisting of isolated points).

When the discrete component takes a …

Doped And Chemically Transformed Transition Metal Dichalcogenides (Tmdcs) For Two-Dimensional (2d) Electronics, Sagar Prasad Paudel

Wayne State University Dissertations

Transition metal dichalcogenides (TMDCs) as the semiconductor counterparts of gra-phene have emerged as promising channel materials for flexible electronic and optoelectronic devices. The 2D layer structure of TMDCs enables the ultimate scaling of TMDC-based devices down to atomic thickness. Furthermore, the absence of dangling bonds in these materials helps to form high quality heterostructures with ultra-clean interfaces. The main objective of this work is to develop novel approaches to fabricating TMDC-based 2D electronic devices such as diodes and transistors. In the first part, we have fabricated 2D p-n junction diodes through van der Waals assembly of heavily p-doped MoS2 (WSe2) …

Integrated Strategies For Sustainable Wastewater-Based Algal Biofuel Production And Environmental Mitigation In The Us, Javad Roostaei

Wayne State University Dissertations

Integration of algae cultivation with wastewater treatment has received increasing interest as a cost-effective strategy for biofuel production. However, there has been no full assessment of algal biofuel production with wastewater on macro-scale by taking into account wastewater resources, land availability, CO2 emission resources, and geographic variation. This research addressed and evaluated the use of wastewater for algae cultivation, in terms of modeling and laboratory experiments. The first goal of this research was to develop a spatially explicit lifecycle model, by integrating life cycle assessment (LCA), and Geographic Information Systems (GIS) analysis, for the evaluation of the environmental and economic …

Modification Of 4,5- Aminoglycosides To Overcome Drug Resistance Bacteria And Toxic Side Effect, Guanyu Yang

Wayne State University Dissertations

ABSTRACT

MODIFICATION OF 4,5- AMINOGLYCOSIDES TO OVERCOME DRUG RESISTANCE BACTERIA AND TOXIC SIDE EFFECT

by

Guanyu Yang

September 2018

Advisor: Professor David Crich

Major: Chemistry

Degree: Doctor of Philosophy

Infectious diseases causing by antibiotic resistant pathogen are one of the major threat to human health and society today. Many researchers tried to develop next generation of antibiotics by reinvesting the existing antibacterial drugs. Aminoglycosides have long been used as highly potent and broad-spectrum antibiotics for treating bacterial infections. But their side effect, especially the irreversible ototoxicity, and the fast-growing resistant problem limit their application. The goal of this research was …

Mixture Models With Grouping Structure: Retail Analytics Applications, Haidar Almohri

Wayne State University Dissertations

Growing competitiveness and increasing availability of data is generating tremendous interest in data-driven analytics across industries. In the retail sector, stores need targeted guidance to improve both the efficiency and effectiveness of individual stores based on their specific location, demographics, and environment. We propose an effective data-driven framework for internal benchmarking that can lead to targeted guidance for individual stores. In particular, we propose an objective method for segmenting stores using a model-based clustering technique that accounts for similarity in store performance dynamics. It relies on effective Finite Mixture of Regression (FMR) techniques for carrying out the model-based clustering with …

Progress Toward Controlled Disulfide Formation To Access Neuroactive Conotoxins, Thilini Kondasinghe

Wayne State University Dissertations

"Conotoxins are mini proteins isolated from marine snails of the Conus family. They have shown activity in the selective inhibition of various ion channels. Therefore, they present an opportunity as possible therapy for a myriad of neurological ailments. The synthesis of conotoxins would enable both biological studies and evaluation of these structures as lead targets for therapeutics. However, establishing a reliable method to consistently folding disulfide rich proteins, including conotoxin, into their native structure has been challenging over few decades. In this research project, it is shown the progress towards a mild, efficient, and broadly applicable methods to generate the …

Carbohydrate-Based Inducers Of Cellular Stress For Targeting Cancer Cell Metabolism, Fidelis Ndombera

Wayne State University Dissertations

ABSTRACT

CARBOHYDRATE-BASED INDUCERS OF CELLULAR STRESS FOR TARGETING CANCER CELL METABOLISM

by

FIDELIS TOLOYI NDOMBERA

May 2018

Advisor: Dr. Young-Hoon Ahn

Major: Chemistry (Biochemistry)

Degree: Doctor of Philosophy

Metabolic reprogramming and redox control of cancer cells is vital for their proliferation, but also provides selective strategies for treating cancer. Increased generation of reactive oxygen species (ROS) and an intricate control of redox status in cancer cells relative to normal cells provide a basis for designing ROS-inducing anticancer agents. In my work, I designed, synthesized and evaluated carbohydrate-based small molecules for ROS-generation, cytotoxicity and redox signaling and stress response. Our data …

Monotonicity Of Set-Valued Mappings And Full Stability Of General Parametrical Variational Systems, Dat Pham

Wayne State University Dissertations

The dissertation introduces and studies the notions of Lipschitzian and Holderian full stability of solutions to three-parametric variational systems described in the generalized equation formalism involving nonsmooth base mappings and partial subgradients of prox-regular functions acting in Hilbert spaces. Employing advanced tools and techniques of second-order variational analysis allows us to establish complete characterizations of, as well as directly variable sufficient conditions for, such full stability properties under mild assumptions. Furthermore, we derive exact formulas and effective quantitative estimates for the corresponding moduli.

Scalable And Secure Provenance Querying For Scientific Workflows And Its Application In Autism Study, Fahima Amin Bhuyan

Wayne State University Dissertations

In the era of big data, scientific workflows have become essential to automate scientific experiments and guarantee repeatability. As both data and workflow increase in their scale, requirements for having a data lineage management system commensurate with the complexity of the workflow also become necessary, calling for new scalable storage, query, and analytics infrastructure. This system that manages and preserves the derivation history and morphosis of data, known as provenance system, is essential for maintaining quality and trustworthiness of data products and ensuring reproducibility of scientific discoveries. With a flurry of research and increased adoption of scientific workflows in processing …

Addressing The Threat Of Multidrug Resistant Infectious Diseases By Synthesis Of Novel Aminoglycoside Antibiotics, Girish Chandra Sati

Wayne State University Dissertations

The ever-growing increase in multidrug resistant infectious diseases is one of the major cause of human mortality, and there is an inherent need for the development of new antibiotics. Since the discovery of streptomycin, AGAs have been playing a very important role in human therapy as highly potent broad-spectrum antibiotics and are listed as one of the critically important antimicrobials by WHO. AGAs act by inhibiting the bacterial protein synthesis and by targeting the A-site present in the small subunit of bacterial ribosome. The clinical use of AGAs is somewhat restricted due to their toxic effects (ototoxicity and nephrotoxicity) and …

Evaluating The Effectiveness Of Biochar For Treating Wsu Parking Lot Runoff, Alan-Christian Thomas

Research Opportunities for Engineering Undergraduates (ROEU) Program 2017-18

Various pollutants including pesticides, herbicides, automotive fluids, and excess nutrients from fertilizers are found in high concentrations in urban runoff. There are many technologies that can be used to control and redirect the water flow such as retention basins, constructed wetlands, and rain gardens; however, these methods are specifically focused on controlling water and not necessarily the nutrients and contaminants in the water. There has recently been an increased interest in the potential for using additional materials (e.g., compost, charcoal) to enhance the pollution treatment ability by either adding them to the soil or by engineering prefilters to remove pollutants …

Evaluating The Effectiveness Of Bioswales In Southeast Michigan, Grace Crowe

Research Opportunities for Engineering Undergraduates (ROEU) Program 2017-18

Bioswales are modern storm water management structures that utilize biological components in a traditional wale to more effectively filter out contaminants. Because of its modern nature the installation and management practices for bioswales is still developing. Perfecting the practices surrounding bioswales in southeast Michigan environment can aid in the advancement of green infrastructure in the state. Wayne State installed a bioswale in one its parking lots in New Center with the help of the Detroit Biodiversity Network (DBN). We wanted to monitor the progression of this existing bioswale throughout the year, observing the system components effecting overall bioswale performance. The …

Stereoselective Synthesis Of Legionaminic Acid And Pseudaminic Acid Glycosides, Bibek Dhakal

Wayne State University Dissertations

Legionaminic acid (Leg) and pseudaminic acid (Pse) are deoxy acetamido analogues of the most common sialic acid, N-acetylneuraminic acid (NeuAc) that are found in microorganisms. Leg and Pse are rare but important class of sialic acids, as their glycosides are found in lipopolysaccharides and glycoproteins of several pathogenic Gram-negative bacteria including Pseudomonas aeruginosa, Legionella pneumophila serogroup 1, Campylobacter jejuni, and Campylobacter coli. As such, the stereoselective glycosylation of the equatorial Leg and Pse donors, and the role played by their side chain conformations in anomeric reactivity and selectivity are the focus of this thesis.

Chapter two describes the synthesis of …