Chemistry Commons^™

Transition Metal Alkoxide Complexes Synthesis Using Thallium Reagents And Design Of Iron(Ii)-Alkoxide Carbene Complexes And Their Reactivity, Lakshani Wathsala Kulathungage

Wayne State University Dissertations

ABSTRACTTRANSITION METAL ALKOXIDE COMPLEXES SYNTHESIS USING THALLIUM REAGENTS AND DESIGN OF IRON(II)-ALKOXIDE CARBENE COMPLEXES AND THEIR REACTIVITY by LAKSHANI WATHSALA KULATHUNGAGE May 2025 Advisor: Dr. Stanislav Groysman Major: Chemistry (Inorganic) Degree: Doctor of Philosophy

This dissertation focuses on the synthesis and reactivity of transition metal and main group metal alkoxide complexes. The dissertation began with exploring a novel, efficient synthetic route towards transition metal alkoxides involving thallium reagents. A novel dimeric Tl2(OCtBu2Ph)2 complex was synthesized in the reaction between a lithium alkoxide and thallium precursor TlPF6. Tl2(OCtBu2Ph)2 served as a convenient precursor to the formation of old and new transition …

Structural Impacts Of Canonical And Non-Canonical Oligonucleotide Modifications, Deepak Shrestha

Wayne State University Dissertations

Nucleic acids, including DNA (deoxyribonucleic acid) and RNA (ribonucleic acids), are the fundamental building blocks of living organisms. The events that cause modification of DNA/RNA are of interest because they impact the nucleic acid function. Targeting DNA is important for treating diseases such as cancer. Cisplatin (cisPt) is a well-studied drug that targets DNA and blocks replication, but its use is limited by adverse side effects and cellular resistance. Prevoius research addressed some of these challenges through development of platinum analogues such as carboplatin and oxaliplatin. Amino acid-linked platinum analogues (AAPt) are the focus of this thesis work. AAPt complexes …

Mass Spectrometry Combined With Chemical Biology To Study Human Ailments, Eric Thomas Jacquerio Davis

Wayne State University Dissertations

Post-translational modifications (PTMs) are essential as chemical changes that regulate protein function, activity, stability, interactions, and localization after protein synthesis. PTMs, such as phosphorylation, acetylation, and ubiquitination, can activate or deactivate proteins, influence their interactions with other molecules, and determine their cellular location. This regulation is vital for numerous biological processes, such as cell cycle control, signal transduction, and gene expression. Abnormal PTMs are linked to various diseases in humans, including parasitic infection, blood disorders, cancers, and neurodegenerative diseases, making their study crucial for understanding disease mechanisms and developing targeted therapies. In the Pflum lab, we are interested in the …

Efficient Sabre-Sheath Hyperpolarization Of Pyruvate And Other Alpha-Ketocarboxylates And Ultra-High-Qualityfactor Wireless Masing Magnetic Resonance Sensing Of Hyperpolarized Contrast Media, Isaiah Olabisi Adelabu

Wayne State University Dissertations

Over the years, there has been research geared towards mitigating disease conditions such as cancers and tumors by molecular sensing of their aberrant metabolism in humans and animal models of diseases. Some of these biomolecules of interest are pyruvate, α-ketoglutarate, and ketoisocaproate, that play a central role in eukaryotic and human metabolic pathways. Nuclear magnetic resonance (NMR) spectroscopy and magnetic resonance imaging (MRI) have become predominant in investigating and imaging cancers and tumors for early detection and treatment. Although conventional NMR spectroscopy is limited by low sensitivity, we overcame this barrier through the use of hyperpolarization techniques. NMR hyperpolarization improves …

Development Of Microfluidic Thermal Gel Electrophoresis For Biological Analysis, Mario Ambrocio Cornejo

Wayne State University Dissertations

ABSTRACTDEVELOPMENT OF MICROFLUIDIC THERMAL GEL ELECTROPHORESIS FOR BIOLOGICAL ANALYSIS by MARIO AMBROCIO CORNEJO May 2024 Advisor: Dr. Thomas H. Linz Major: Chemistry (Analytical Chemistry) Degree: Doctor of Philosophy The molecular biology that takes place within cells is vital to the over function of an organism. Healthy cellular function is crucial to a wide web of interconnected processes that need to be balanced and regulated. When these processes become abnormal, disease states are developed. The mapping of biological networks has led to the development of gene therapy and more accurate diagnostic tests. However, there are still vital biomolecules that due to …

Exploiting Light To Probe Biological Processes, Madeline Denison

Wayne State University Dissertations

Metal complexes have many advantages as biochemical tools due to their rich photophysical properties and unique geometry. Metal-based complexes are commonly reported as emissive probes or photoactivatable biological agents. Long emission lifetimes of metal complexes allow for the use of lifetime gating which eliminates autofluorescence found in assays, a distinct advantage over short-lived organic fluorophores. This work utilizes this powerful technique to generate reversible, emissive probes for monitoring CYP3A4 active site occupancy. In addition to the emissive properties of metals, metals can also be used as photodynamic therapy (PDT) and photochemotherapy (PCT) agents. These light-activated strategies provide important spatiotemporal control …

Visible Light Photocatalysis With Quantum Dot Gel For Organic Synthesis, Daohua Liu

Wayne State University Dissertations

This dissertation presents metal chalcogenide quantum dots (QDs), a group of emerging visible light photocatalysts, for unique organic chemical transformations that are impossible using conventional molecular photocatalysts. The first part of this dissertation focuses on the comparison between ligand-capped CdS QD and CdS gel. CdS QD gel is a three-dimensional network of interconnected QD. CdS gels were found to show more facile charge transfer with substrates than QDs, due to the partial removal of ligands from its surface during gelation. Our study showed that the photocatalytic activity of CdS gels was indeed superior to trioctylphosphine (TOP)- and thioglycolic acid (TGA)-capped …

Thermosensitive Phosphors As Optical Temperature Sensors In Extreme Environments, Marcos Ramon Imer Rocha Pita

Wayne State University Dissertations

Luminescent temperature sensors offer unique advantages over thermocouples and pyrometers for applications in extreme environments such as operando wall temperature mapping of combustion engines. A refractory oxide host doped with an optically active ion has the potential to afford a thermosensitive phosphor with a well-defined temperature response in such extreme environments. However, the design of thermosensitive phosphors with targeted temperature sensitivity and spatial resolution in the operational temperature range of interest has been hindered by the inability to rationally select host–activator pairs. A major scientific question is what crystal-chemistry features a low thermal conductivity oxide must possess to afford a …

Density Functional Studies Of Molecular Separation And Charge Transport, Timothy Quainoo

Wayne State University Dissertations

This thesis presents a series of studies which can be grouped majorly into two sections both focusing on the utilization of density functional theory techniques; Molecular electronics and Molecular separation. Molecular electronics has been anticipated to hold a great future as it seeks to apply molecular building blocks in the creation of electronic components. On the other hand, the utilization of mild conditions in chemical processes is geared toward the major goals of green chemistry as it produces less waste and is cost-effective. Thus, this dissertation tackles and answers some of the unanswered questions in literature by using theoretical methods …

Design And Synthesis Of Aminoglycoside-Based Heparan Sulfate Mimetics For Structure-Activity Relationship Studies Of Heparan-Binding Proteins, Joseph Wakpal

Wayne State University Dissertations

Cancer remains a formidable challenge in modern medicine, demanding innovative approaches and treatments. Among the emerging strategies, inhibiting heparanase and fibroblast growth factor 2 (FGF2) has garnered considerable attention in recent years. This dissertation presents a novel approach to designing and synthesizing a diverse library of heparan sulfate (HS) mimetics derived from aminoglycosides to study their binding to two heparin-binding proteins involved in cancer development and metastasis. Heparanase cleaves HS polysaccharide chains in the extracellular matrix (ECM) and is a regulator of aggressive tumor behavior. Clinical studies have illustrated that aberrant heparanase expression correlates with increased tumor size, amplified tumor …

Probing Microscopic Properties Of Next Generation Materials Using Coherent Vibrational And Electronic Spectroscopy, S Mudiyanselage Sachithra Tikiri Kumara Wanasinghe

Wayne State University Dissertations

The dissertation research focused on understanding the relationship between the chemical structure of organic molecules and their photophysical properties, particularly examining coherent electronic and vibrational coupling within and between molecules, with implications for next-generation energy technologies. In Chapter 2, we employed both steady-state and transient optical and magnetic spectroscopic techniques to understand the electronic delocalization in both singlet and triplet exciton delocalization in weakly bound porphyrin dimeric molecules. Our results highlight that the delocalization of singlet exciton delocalization does not guarantee the delocalization of triplet excitons between weakly bound porphyrin macromolecules. Our studies demonstrate how one can access the electronic …

Design, Synthesis, And Evaluation Of Class Iia Histone Deacetylase (Hdac) Inhibitors, Lauren Nicole Kotsull

Wayne State University Dissertations

Histone deacetylase (HDAC) proteins are linked to disease states, including cancer, and have become important targets for therapeutic development. Many inhibitors have been developed to target HDAC proteins, including FDA-approved inhibitors Vorinostat (SAHA), Belinostat, Romidepsin, and Panobinostat. These inhibitors non-specifically influence most of the 11 metal-dependent HDAC isoforms, which might contribute to the side effects that patients experience during treatment. The lack of selectivity also diminishes the use of HDAC inhibitors as biomedical research tools. To address these drawbacks, the development of selective inhibitors has been heavily studied. Yet, reported inhibitors are predominantly selective for class I HDAC isoforms (HDACs …

Exploration Of Electron Dynamics In A Strong Field By Time Dependent Configuration Interaction With A Complex Absorbing Potential, Paul Hoerner

Wayne State University Dissertations

Strong field electron dynamics are a quickly developing field of study in physical chemistry. In order to better understand experimental observations, there is a need for computational tools to simulate electron dynamics in a strong field. Due to the nature of strong electric fields, this requires the solving of the time dependent Schrödinger equation (TDSE). Various methods have been used to solve the TDSE in a strong field. In order to look at molecular systems while accurately treating the underlying physics, a method that balances computational affordability with theoretical rigor is necessary. The chosen method that matches these criteria is …

Alternating Current Electrolysis For Amine Functionalization And Hydrogen Isotope Exchange, Disni Gunasekera

Wayne State University Dissertations

Electrochemical organic synthesis is experiencing a renaissance driven by the increasing demand for green chemistry and engineering in the pharmaceutical industry. Synthetic organic electrochemical methods can be divided into three types: anodic, cathodic, and paired electrolysis. Paired electrolysis, in which two desirable half-reactions are performedsimultaneously at the two electrodes, is mostly underdeveloped. However, paired electrolysis can be technologically significant because it not only improves energy efficiency by using both electrodes but also provides a unique reaction environment where two redox-opposite reactions of substrates take place in the same pot. A major challenge for paired electrolysis is that the difficulties associated …

Synthesis Of Putative Microcystin-Lr Degradation Products And Full Macrocyclic Cyanopeptide, Mahesh Kumar Yadab

Wayne State University Dissertations

This thesis primarily focuses on synthesizing fragments of microcystin-LR, which is a natural product, with the aim of establishing them as analytical standards for investigating the biodegradation pathways of MC-LR. Despite of the substantial interest in synthesizing, isolating, and degrading Microcystins over the past few decades, the availability of high-purity microcystin standards at known concentration for quantitative analysis of using LC-MS/MS remains limited. The synthesis of the proposed MC-LR fragments employs the Fmoc/t-Bu protecting group strategy to prevent isomerization. Additionally, novel methods for the total synthesis of N-Boc-Adda are explored, incorporating atom-economic approaches, cross-metathesis, and oxidative boron Heck reactions. The …

Lanthanide-Based Responsive Contrast Agents For Magnetic Resonance Imaging, Md Mamunur Rashid

Wayne State University Dissertations

This thesis is a collection of seven chapters that discuss the contributions to the field oflanthanide-based contrast agents for magnetic resonance imaging (MRI), particularly in the context of imaging hypoxia and extracellular pH. These physiological changes play a significant role in life-threatening conditions such as cancer, making it essential to develop effective imaging tools to aid in diagnosis and treatment. The thesis provides insights for the rational development of lanthanide-based contrast agents for MRI. A comprehensive review of divalent europium as a tool for imaging hypoxia using magnetic resonance imaging and how coordination chemistry can be used to tune the …

Synthesis And Reactivity Of Xanthene-Based Heterobimetallic Systems For Co Oxidation, Umesh Kaluarachchige Don

Wayne State University Dissertations

Nature provides a useful guideline for the design of an efficient earth-abundant catalyst for CO oxidation that relies on bimodal heterobimetallic cooperativity. Molybdenum-copper carbon monoxide dehydrogenase (Mo-Cu CODH) is an enzyme of the xanthine oxidoreductase family that catalyzes reversible oxidation of CO; it is inhibited by cyanide CN- and inserts isocyanide CNR between Cu and O/S. The active site contains molybdenum(VI) in a square pyramidal configuration with apical oxo and basal dithiolene, oxo, and sulfide ligands. The two-coordinate Cu(I) is coordinated by cysteinate and Mo-sulfide to form Mo-S-Cu bridge.While several groups have reported structural models of the active site of …

Cryptand-Based Low-Valent F-Block Complexes Toward Stabilization And Separation Of Actinides And Lanthanides, Deshika Nuwangi Kulasekara

Wayne State University Dissertations

ABSTRACTCRYPTAND-BASED LOW-VALENT F-BLOCK COMPLEXES TOWARD STABILIZATION AND SEPARATION OF ACTINIDES AND LANTHANIDES DESHIKA NUWANGI KULASEKARA August 2023 Advisor: Dr. Matthew J. Allen Major: Chemistry (Inorganic) Degree: Doctor of Philosophy This thesis consists of six chapters that include studies of the understanding of ligand environment on the stabilization and separation of low-valent lanthanides and actinides. The studies explain the trends in structural, spectroscopic, and electrochemical properties of lanthanide and actinides with respect to changes in donor atoms, denticity, basicity, and counter ions. This dissertation also discusses a ligand-modified solid–liquid extraction method to separate lanthanide from each other. A brief overview of …

Testing Different Approaches For The Stabilization Of Mdi: Design Of Low-Valent Molybdenum Complexes In Redox-Active Environments And Capture-Release Reactions Using N-Heterocyclic Carbenes, Asanka Indrajith Dissanayake

Wayne State University Dissertations

Methylene diphenyl diisocyanate (4,4’-MDI) is an aromatic diisocyanate, which is widely used as a monomer in the polyurethane industry. One of the main challenges with using 4,4’-MDI is its dimerization into uretdione. The polyurethane industry seeks solutions that could suppress dimerization of 4,4’-MDI and extend its shelf-life. The focus of this dissertation is on the design of chemical solutions to this problem including: (1) reversible coordination of MDI (heteroallene) to low-valent mono- or dimolybdenum complexes in redox-active ligand environment, and (2) reversible coordination of MDI with two equivalents of an appropriate N-heterocyclic carbene.

MDI (isocyanate) is a heteroallene, and heteroallenes …

Hyperpolarized Nitrogen-15 Mri Contrast Agents For Hypoxia Sensing Via Reversible Exchange With Parahydrogen, Mohammad Shah Hafez Kabir

Wayne State University Dissertations

The detection of hypoxia in hypoxic-related diseases can provide crucial information for treatment planning and assessment of therapy response. Although Positron Emission Tomography (PET) was employed as a research tool for imaging of hypoxia detection, it has several limitations. Our motivation is to develop a hyperpolarized (HP) molecular probe for hypoxia sensing. My dissertation presents the utility of Signal Amplification By Reversible Exchange in SHield Enables Alignment Transfer to Heteronuclei (SABRE-SHEATH) to hyperpolarize a wide range of N-heterocyclic compounds, which can be employed as MRI contrast agents for hypoxia sensing and other molecular imaging applications.SABRE-SHEATH is a rapid, simple, cost-effective …

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 …

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 …

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 …

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 …

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 …

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 …

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, …

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, …

Atomic Layer Deposition (Ald) Of Lanthanide Oxide Films: Synthesis, Characterization, And Precursor Property Evaluation Of New Classes Of Lanthanide Complexes And Thermal Ald Of Erbium Oxide Thin Films, Navoda Amali Jayakodiarachchi

Wayne State University Dissertations

ATOMIC LAYER DEPOSITION (ALD) OF LANTHANIDE OXIDE FILMS: SYNTHESIS, CHARACTERIZATION, AND PRECURSOR PROPERTY EVALUATION OF NEW CLASSES OF LANTHANIDE COMPLEXES AND THERMAL ALD OF ERBIUM OXIDE THIN FILMSby NAVODA AMALI JAYAKODIARACHCHI August 2022 Advisor: Prof. Charles H. Winter Major: Chemistry (Inorganic) Degree: Doctor of Philosophy Lanthanide oxide-containing thin films are groups of materials with high application potential in numerous fields, including microelectronic, photovoltaic, catalysis, and surface-coating applications. These oxides are refractory materials with high melting points and thermodynamic stabilities, hence, are useful as heat and corrosion-resistant coatings. Further, due to the high refractive indices of lanthanide oxides, they are widely …

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 …