Chemistry Commons^™

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 …

Investigating Spatiotemporal Kinetics, Dynamics, And Mechanism Of Exosome Release, Anarkali Mahmood

Electronic Theses and Dissertations

Exosomes are small lipid-based vesicles that can carry biomolecules from one cell to another. While exosomes are crucial to maintain homeostasis in healthy cells, they are exploited by unhealthy cells to aid disease progression. Exosomes likely facilitate disease progression via the transfer of disease-causing biomolecules from unhealthy to healthy cells. Exosomes are generated in Multivesicular endosomes (MVEs) and are then secreted into the extracellular space to travel to other cells. Despite being a crucial step, very little is known about exosomes release mechanism and dynamics. To further our understanding of exosomes, specifically their secretion, my work has focused on investigating …

Benzothiazole-Substituted Boron Difluoride Formazanate Dyes, Francis L. Buguis, Paul D. Boyle, Joe B. Gilroy

Chemistry Publications

The incorporation of benzothiazole heterocycles into existing molecular frameworks has resulted in the production of a wide range of multifunctional molecular materials. However, this strategy has not yet been explored for an emerging class of boron difluoride dyes, derived from formazanate ligands, which often exhibit tuneable redox and optical properties. Here, we address this gap in the literature and describe the synthesis and characterization of a series of benzothiazole-substituted BF­₂ formazanates. The incorporation of benzothiazole resulted in absorption profiles that were shifted to lower energies and reduction events that were shifted to more positive potentials when compared to those …

Selective Reduction Of Nitriles In The Presence Of Aromatic Nitro Groups, Jeffrey D. Amidon, Michael Barbachyn

Summer Research

• Establish proof of concept and define optimal conditions for an aprotic reduction of a nitrile.
• Examine a range of compounds to determine the scope of the optimal conditions.

Investigating Alamethicin Ion Channel Behavior In Lipid Bilayers, Vennisa Owusu-Barfi, Loren Haarsma

Summer Research

Lipid molecules are made up of a head group that is strongly attracted to water and a tail group that is less attracted to it. In water, they selfassemble into bilayers which form the basis of cell membranes. Ion channels are proteins in the lipid bilayer which control the flow of ions in and out of the cell. Alamethicin is a 20 amino-acid peptide produced by fungus. When added to a lipid bilayer they self-assemble into voltage-dependent ion channels which open for brief periods called dwell times, usually on order of a few milliseconds. Because alamethicin is a fairly simple …

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 …

Biomedical Applications Of Lanthanide Nanomaterials, For Imaging, Sensing And Therapy, Qize Zhang, Stephen O'Brien, Jan Grimm

Publications and Research

The application of nanomaterials made of rare earth elements within biomedical sciences continues to make significant progress. The rare earth elements, also called the lanthanides, play an essential role in modern life through materials and electronics. As we learn more about their utility, function, and underlying physics, we can contemplate extending their applications to biomedicine. This particularly applies to diagnosis and radiation therapy due to their relatively unique features, such as an ultra-wide Stokes shift in the luminescence, variable magnetism and potentially tunable properties, due to the library of lanthanides available and their multivalent oxidation state chemistry. The ability to …

Developing A New Treatment For Superficial Fungal Infection Using Antifungal Collagen-Hsaf Dressing, Jing Zhong, Xiayi Yan, Xin Zuo, Xuan Zhao, Jiahui Yang, Qin Dou, Lulu Peng, Yuxiang Zhu, Yichen Xiao, Zeran Bian, Dalian He, Qiushuang Xu, Stephen Wright, Yaoyao Li, Liangcheng Du, Yan Wang, Jin Yuan

Department of Chemistry: Faculty Publications

Fungal pathogens are common causes of superficial clinical infection. Their increasing drug resistance gradually makes existing antifungal drugs ineffective. Heat stable antifungal factor (HSAF) is a novel antifungal natural product with a unique structure. However, the application of HSAF has been hampered by very low yield in the current microbial producers and from extremely poor solubility in water and common solvents. In this study, we developed an effective mode of treatment applying HSAF to superficial fungal infections. The marine-derived Lysobacter enzymogenes YC36 contains the HSAF biosynthetic gene cluster, which we activated by the interspecific signaling molecule indole. An efficient extraction …

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 …

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 …

Evaluation Of A Shortened Redon Fit Test Protocol For Half-Mask Respirators, Olivia Dawson, Riley Duncan, Leshan J. Kimbrough

Scholar's Day

The purpose of this study was to investigate whether a shortened REDON method is as effective and accurate compared to the reference method when measuring respirator fit for elastomeric half-mask respirators using the Quantifit® CNP instrument.

Sequential Assembly Of 1-D And 2-D Origami Arrays, Nathan Shin

Theses, Dissertations and Capstones

DNA origami, invented by Paul Rothemund in 2006, provides many possible routes for the synthesis of complex macromolecular assemblies. This project involves the creation of 1-D and 2-D arrays of cross origami to support the development of DNA detection devices by providing precise platforms for these devices. The M13 plasmid is the most commonly used scaffold in DNA nanotechnology, limiting the size and complexity of an individual DNA origami construct. However, by creating larger assemblies, the dimensions can be multiplied. For example, by alternating two different types of cross origami, optical reporters can be separated by 200 nm, which is …

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 …

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 …

Investigation Of Catalysis Of Nitration By Cytochrome P450s, Lannika Johnson

Honors Undergraduate Theses

TxtE is a protein related to cytochrome P450 enzymes, which catalyze a number of reactions that typically involve oxygen and not nitrogen. It has been discovered that TxtE can nitrate tryptophan through an unusual reaction in which it uses nitric oxide (NO) as a nitrogen donor to install the nitro group despite NO typically being considered toxic to bacteria. This project will determine if all cytochromes P450 can catalyze nitration as long as they are given NO. This will have an impact on understanding drug delivery and metabolism for which nitration is important.

Synthesis And Characterization Of Silver-Gold Nanocage With Enhanced Thermal Stability, Victoria Ten

Honors Undergraduate Theses

Silver-gold nanocages have attracted considerable research interest recently due to their excellent performance in the fields of biomedicine and photocatalysis. These applications oftentimes manipulate at elevated temperatures and therefore impose demands on the thermal stability of the cage structures. To better understand this subject, in this work, we systematically evaluated the thermal stability of two nanocages with different wall thicknesses of 3.8 nm and 13 nm, both in the solution-phase (diethylene glycol) and solid-phase (in-situ STEM). The results revealed that the nanocages with thicker walls exhibited better thermal stabilities in both phases. By monitoring and analyzing the morphology changes of …

Whole Exome Sequencing Identifies A Novel Mutation In Aspm And Ultra-Rare Mutation In Cdk5rap2 Causing Primary Microcephaly In Consanguineous Pakistani Families, Ehtisham Ul Haq Makhdoom, Haseeb Anwar, Shahid Mahmood Baig, Ghulam Hussain

Department of Biological & Biomedical Sciences

Background & objectives: Primary Microcephaly (MCPH) is a rare neurogenetic disease, manifesting congenitally reduced head circumference and non-progressive intellectual disability (ID). To date, twenty-eight genes with biallelic mutations have been reported for this disorder. The study aimed for molecular genetic characterization of Pakistani families segregating MCPH.
Methods: We studied two unrelated consanguineous families (family A and B) presenting >2 patients with diagnostic symptoms of MCPH, born to asymptomatic parents. We employed whole-exome sequencing (WES) of probands to find putative causal mutations. The candidate variants were further confirmed and analyzed for co-segregation by Sanger sequencing of all available members of each …

Surface Engineering For Controlled Growth And Deposition Of Nanomaterials - Assembly And Design At The Nano-Microscale, David Fox

Electronic Theses and Dissertations, 2020-2023

Materials with nanoscale dimensions offer several important benefits over bulk materials (e.g. increased surface area, low-cost, deviation from bulk properties, etc.). Such materials are critical components for next-generation energy storage materials, optoelectronic devices, and catalyst systems. However, these materials are often processed in liquid media, and their diminutive structures are fragile in the presence of capillary forces. As such, preparing uniform and stable nanomaterial coatings is a significant challenge. Herein, we discuss an approach where the substrate itself is factored into the assembly and growth of these materials. First, nanoporous surfaces were utilized to achieve a uniform deposition of one-dimensional …

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 …

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 …

The Effect Of Autophagy Related Protein 10 And Its Mutants On Autophagic Activity, Sk Nadia Rahman Silvia

Senior Honors Theses and Projects

Autophagy is the cellular degradation process in which cellular contents are encapsulated by double-membrane vesicles, autophagosomes, and delivered to the vacuole to be degraded and recycled. This process is important for cell health and homeostasis. There are approximately 32 different autophagy-related proteins involved. Atg10 is an enzyme that may affect overall autophagic activity by changing autophagosome size and/or number. Our goal is to find mutants that cause a significant, partial loss in Atg10’s activity by mutating some residues near the active site and testing the functionality of these mutants by performing western blots and enzymatic assays. Here we show that …

Introducing An H113a Mutation Into Atg10 Y73q To Reduce Autophagic Activity And Understand The Effect Of Atg On Autophagosome Size And Number, Konrad L. Lautenschlager

Senior Honors Theses and Projects

Autophagy is an essential recycling process that occurs within eukaryotic cells, however, the individual functions of the current thirty-two known autophagic proteins are not yet entirely understood. At this time, it is known that the autophagic protein Atg7 works upstream of both Atg3 and Atg10. Atg3 is affected by Atg7 and allows for the attachment of Atg8 and the lipid PE which is part of the autophagosome membrane. The Atg10 pathway is also affected by Atg7 but attaches Atg12 to Atg5 which upregulates the function of Atg3 and ultimately Atg8 lipidation. These protein interactions are necessary for forming autophagosomes, large …

Photophysical, Electrochemical, And Catalytic Studies Of Anthraquinone And Pyridoxyl-Based Sensors And Development Of Ruthenium Photosensitizers, Anwar Hussain

Dissertations and Theses

In the past, we have demonstrated the photophysical properties of several anthraquinone derivatives that act as a luminescent host for various environmental and biological cations. Here we extend our expertise in photochemistry to the class of chemicals containing the pyridoxal moiety. Several ligands were synthesized using eco-friendly, simple, one-step reactions via Schiff base and condensation reactions. The optical properties of these ligands were examined with a series of cations. We demonstrated the ability to detect the biologically important zinc ion in living cells such as RAW 264.7 and HEK 293 via fluorescence signaling. In addition, we extend our explorations to …

Chromatographic Studies Of Some Hormone And Metabolic Modulators Used For Doping In Sports, Ruth Marie Speidel

Online Theses and Dissertations

The World Anti-Doping Agency (WADA) is an international agency that monitors the use of Performance Enhancing Drugs (PEDs) in sports; their mission is “to lead a collaborative worldwide movement for doping-free sport” (Who We Are, 2022). For this mission, the WADA needs quick, sensitive, reproducible, and accurate methods for analyzing athletes’ biological fluids for possible PEDs. This research focuses on developing and validating simple, sensitive, rapid, and reliable gas chromatography- mass spectrometry (GC-MS) methods for the analysis of two hormone and metabolic modulators, toremifene and trimetazidine. Previously, there has been limited GC-MS methods used to analyze toremifene and trimetazidine. Quantification …