Chemistry Commons^™

Synthesis Of Phosphonate-Based Diimide Ligands, Kenya V. Medina

Honors Program Theses and Research Projects

There has been a resurged interest in the synthesis of metal-organic frameworks because of their potential applications in energy production and drug delivery. Although diimides are insoluble in aqueous solutions, the addition of phosphonic acid allows the complex to be water soluble, which greatly increases their application. Therefore, the creation of a hybrid metal-organic complex by the addition of phosphonic groups to diimide ligands can result in a polar porous compound. In this project the ligand design included the use of dianhydrides including pyromellitic dianhydride, naphthalenetetracarboxylic dianhydride, perylenetetracarboxylic dianhydride, and biphenyl-tetracarboxylic acid dianhydride. These dianhydride precursors were refluxed under argon …

Transition Metal Phosphides For High Performance Electrochemical Energy Storage Devices, Amina Saleh

Theses and Dissertations

Electrochemical energy storage technologies are nowadays playing a leading role in the global effort to address the energy challenges. A lot of attention has been devoted to designing hybrid devices known as supercapatteries which combine the merits of supercapacitors (high power density) and rechargeable batteries (high energy density). Transition metal phosphides (TMP) are a rising star for supercapattery anode materials thanks to their high conductivity, metalloid characteristics, and kinetic favorability for fast electron transport. Herein, new TMP-based materials were synthesized for use as supercapattery positive electrodes, via a multifaceted approach to yield devices enjoying concurrently high power and energy densities. …

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 …

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 …

Biomimetic Synthesis Of Palladium Nanoparticles For Catalytic Application, Emily A. Groover

College of Graduate Studies: Theses & Dissertations

The synthesis of palladium nanoparticles (Pd NPs) using materials-directed peptides is a novel, nontoxic approach which exerts a high level of control over the particle size and shape. This biomimetic technique is environmentally benign, featuring nonhazardous ligands and ambient conditions. Nanoparticles are extremely reactive catalysts, boasting a large surface-to-volume ratio when compared to their bulk counterparts. The rational design of these nanoparticles using peptides has been very successful in aqueous environments, but no research has been done to apply it in organic systems. As such, the biomimetic synthesis of Pd NPs in an organic system is here investigated, with ethanol …

Pd-Based Photocatalysts For Heck C-C Cross-Coupling Reactions, Suha Ali Alshehri

Masters Theses

Heck C-C cross-coupling reaction has been widely employed in synthetic organic chemistry because of its high efficiency and simplicity, however the conventional Heck C-C cross-coupling reaction conditions involve the use of an expensive toxicant phosphine-ligated palladium complexes, and high temperature. To address these drawbacks, a highly efficient, homogeneous photocatalyst based on BODIPY for the Heck C-C cross-coupling reactions of aryl iodide and methyl acrylate in DMF solvent under inert conditions has been developed. The 4-Py-BDP-Pd, 3-Py-BDP-Pd and, 2-Py-BOD-Pd catalysts were synthesized and purified using column chromatography. The optical properties of products and intermediates were studied by UV/vis absorption and fluorescence …

First Homoleptic Rare Rarth Metal Complexes With Doubly-Reduced Dibenzocyclooctatetraene, James C. Mahoney

Legacy Theses & Dissertations (2009 - 2024)

A set of novel complexes of rare earth elements, M(III) = Y, La, Gd, Tb, and Dy, with the doubly-reduced dibenzo[a,e]cyclooctatetraene (DBCOT) anion has been synthesized and crystallographically characterized for the first time. Preparation of new complexes has been accomplished through the ligand-metathesis reaction of M(III) triiodides with K2(DBCOT) in THF at ambient conditions. Subsequent crystallization via slow solvent evaporation afforded single crystals of good quality. X-ray diffraction technique confirmed that all complexes are isomorphous and conform to the [M(DBCOT)(THF)4][M(DBCOT)2] composition. In their crystal structures, the monoanionic double-decker sandwiches, [M(DBCOT)2], weakly interact with the cationic counterparts, [M(DBCOT)(THF)4]+. In both parts, …

Dirhenium Compounds Containing The Diphosphine Ligands Ph2pch2pph2, Ph2pch(Cn)Pph2, Or Ph2pch(Ch3)Pph2: A Comparative Study, Hannah C. Arthur

Undergraduate Honors Theses

When M₂L₁₀ complexes containing two rhenium(III) atoms in a quadruple bond react with an excess of the diphosphine ligand Ph₂PCH₂PPh₂, the bond order decreases, and the rhenium is reduced to rhenium(II). When two diphosphine ligands are bonded to the dirhenium center, they can adopt a trans-trans, trans-cis, or cis-cis configuration. NMR spectra of compounds that adopt the cis-cis arrangement show unusually large downfield shifts for one of the bridgehead methylene hydrogens (P-CH₂-P). To understand the unusual chemical shift, the hydrogens first have to be assigned. The strategy for …

Pascoite Minerals And Potential Application Of Nmr Spectroscopy, Craig C. Mclauchlan, Beth Trent-Ringer, Debbie C. Crans

Faculty Publications – Chemistry

The 20 minerals encompassing the pascoite family of decavanadate isopolyanion-containing [V₁₀O₂₈]⁶⁻ minerals include a few minerals, such as rakovanite, that have been described as containing a protonated decavanadate anion. Rakovanite was originally assigned the formula Na₃[H₃V₁₀O₂₈]•15H₂O and now is redefined with an ideal formula (NH₄)₃Na₃[V₁₀O₂₈]•12H₂O. Nuclear magnetic resonance (NMR) and particularly ⁵¹V NMR spectroscopy is an informative method used to describe the protonation state and speciation in both solid and solution states …

The Synthesis And Characterization Of Pb(Ii) Cyanoximates, Patricia Mcdaniel

Graduate Theses/Dissertations

A new series of Pb(II) cyanoximates were synthesized and characterized by elemental analysis (C, H, N, S), IR spectroscopy, thermal analysis, and X-ray crystallography. The goal was to synthesize compounds with a PbL₂ (L= selected known chelating cyanoximes) composition for use as potential new non-linear optical (NLO) materials, specifically second harmonic generators (SHG), which must belong to non-centrosymmetric space groups. A desktop procedure using Pb²⁺ is chosen due to its typically active 6s² lone pair of electrons, which are known to distort central polyhedra. A 1:2 ratio of Pb(II) to ligand were used to synthesize bulk products …

Using Powder Diffraction To Give Insight Into Structures Of Ir2(Diisocyanomenthane)4x2 [Dimen] (X = Cl; Pf6; Bph4), Mairead Brownell

Scripps Senior Theses

Ir2(dimen)42+ (dimen = 1,8-diisocyanomenthane) has been studied extensively as model compound to better understand catalysis of photochemical reactions. Although Ir2(dimen)42+ has been used primarily to observe the photophysical changes of metal-metal transitions, it gives great insight into the transitions that allow other d8-d8 metal complexes to undergo photochemical processes and generate hydrogen gas. The large visible range by which Ir2(dimen)42+ (1) can be electronically excited in solution is indicative of its two solution phase ground states, which interestingly have been hypothesized to resemble two unique packing structures observed in the powder state. In this study, the powder diffraction patterns of …

Purification And Activity Assay Optimization Of Bacterial Catalase From Psychrobacter Koprana, Sydney Willis

Honors Program Theses

To date, catalase protein from bacterial species is not the most widely used commercial catalase. Catalase, the enzyme that breaks down hydrogen peroxide in most living organisms, is an invaluable enzyme in the food, agriculture, and pharmaceutical industries. In 2019, a novel species of a psychrotolerant bacterium was discovered in Cold Harbor, NY. This species, Psychrobacter koprana, exhibits highly active catalase. Preliminary data from activity assays demonstrates that P. koprana catalase has the same activity as commercially available catalase. After purification and activity assay optimization, the activity of this catalase has the potential to be more active than other easily …

Multilevel Computational Investigation Into The Dynamics And Reaction Mechanisms Of Non-Heme Iron And 2-Oxoglutarate Dependent Enzymes, Shobhit Sanjeev Chaturvedi

Dissertations, Master's Theses and Master's Reports

Computational chemistry methods have been extensively applied to investigate biological systems. This dissertation utilizes a multilevel computational approach to explore the dynamics and reaction mechanisms of two groups of enzymes belonging to non-heme Fe(II) and 2-oxoglutarate (2OG) dependent superfamily – histone lysine demethylases from class 7 and ethylene forming enzyme (EFE). Chapter 2 uncovers the role of conformational dynamics in the substrate selectivity of histone lysine demethylases 7A and 7B. The molecular dynamics (MD) simulations of the two enzymes revealed the importance of linker flexibility and dynamics in relative orientations of the reader (PHD) and the catalytic (JmjC) domains. Chapter …

Synthesis, Characterization, And Activation Of Pyridine Dipyrrolide Supported Vanadium-Nitrogen Multiple Bonds, Jordan Cruz Martinez

Graduate Theses, Dissertations, and Problem Reports (ETD)

The chemistry of coordination complexes of vanadium supported by pyridine di-pyrrolide pincer ligands was probed via the synthesis and investigation of a variety of compounds from the trivalent starting material, (^MesPDP^Ph)VCl(thf)₂. Under reducing conditions and subsequent addition of terpyridine, a redox transfer series (1-, 0, 1+) stemming from the neutral product (^MesPDP^Ph)V(terpy) was isolated and characterized by X-ray crystallography. The precise bond lengths, in conjunction with bulk magnetic susceptibility, allowed for a detailed study of the redox non-innocence of polypyridyl ligands in these systems.

Metathesis of the halide starting material …

A Study Of Π – Π Stacking Interactions In Rhenium Carbonyl Complexes Based On Backbone Functionalized Bis(Pyrazolyl)Methane Ligands, Balamani Guduru

Masters Theses

π – π Stacking interactions are one of the most important non-covalent inter-molecular forces, which play an important role in the architecture of 1D and 2D networks of supramolecular chemistry. This associative contact involves the attractive interactions of aromatic molecules with each other. To describe and study the strength of the π – π stacking interactions, four new bis(pyrazolyl)ethanamine ligands having different aromatic groups (1-pyrenyl, 1-naphthyl, 2-naphthyl, and 9-anthracenyl) known for their propensity to be involved in π – π stacking interactions were prepared by the reaction of one equivalent of bis(pyrazolyl)ethanamine with one equivalent of the corresponding aromatic aldehyde. …

Synthesis And Characterization Of Ruthenium Complexes And Their Potential And Photosensitizers For Photodynamic Therapy, Keit Dine

Master's Theses

Cancer is one of the leading causes of death in the world with over 10 million people dying of the disease every year. Inorganic complexes supported by platinum metal centers are often used in cancer treatment. However, these complexes lack selectivity for tumor cells. As such, other alternatives to platinum have been explored. Ruthenium (Ru) complexes are one of the most promising candidates due to their ability to be used as photosensitizing drugs in photodynamic therapy. Herein, we report the design, synthesis, and characterization of two novel ruthenium-based complexes. One compound is a Ru(II) homoleptic complex, while the other is …

Modeling, Fabrication, And Characterization Of Rf-Based Passive Wireless Sensors Composed Of Refractory Semiconducting Ceramics For High Temperature Applications, Kavin Sivaneri Varadharajan Idhaiam

Graduate Theses, Dissertations, and Problem Reports (ETD)

Real-time health monitoring of high temperature systems (>500^oC) in harsh environments is necessary to prevent catastrophic events caused by structural failures, varying pressure, and chemical reactions. Conventional solid-state temperature sensors such as resistance temperature detectors (RTDs) and thermocouples are restricted by their operating environments, sensor dimensions and often require external power sources for their operation. The current work presents the research and development of RF-based passive wireless sensing technology targeting high temperatures and harsh environmental conditions. Passive wireless devices are generally classified as near-field and far-field devices based on the interrogation distance. Near-field sensors are placed at …

Electrocatalytic Processes For Energy Storage & Conversion, Apurv Saxena

Doctoral Dissertations

"The continuous excessive usage of fossil fuels has resulted in its fast depletion leading to an escalating energy crisis as well as several environmental issues leading to increased research towards sustainable energy conversion. Electrocatalysts play crucial role in the development of numerous novel energy conversion devices including fuel cells and solar fuel generators.

High-efficiency and cost-effective catalysts are required for large-scale implementation of these new devices. Over the last few years transition metal chalcogenides have emerged as highly efficient electrocatalysts for several electrochemical devices such as water splitting, carbon dioxide electroreduction and, solar energy converters. These transition metal chalcogenides exhibit …

S-Type Stars: Lao Line List For The B²Σ⁺-X²Σ⁺ Band System, P. F. Bernath, Randika Dodangodage, J. Liévin

Chemistry & Biochemistry Faculty Publications

LaO bands are a characteristic feature in the spectrum of cool S-type stars. La is made primarily by the s-process during the asymptotic giant branch phase of stellar evolution. The B²Σ⁺–X²Σ⁺ and A²Π–X²Σ⁺ band systems can be used to determine the La abundances in cool S stars. The bands of the B²Σ+–X²Σ⁺ with v' and v" ⩽ 5 have been rotationally analyzed from an emission spectrum from a carbon furnace. Line strengths are calculated using an ab initio transition dipole …

Electronic Structure Of Early Transition Metal Complexes Supported By Pyridine Polypyrrolide Ligands, Dylan Connor Leary

Graduate Theses, Dissertations, and Problem Reports (ETD)

A thorough study of photoluminescent molecules involving the pyridine polypyrrole(ide) ligand platform has been conducted. A detailed analysis on speciation of the proligand H₂(^MesPDP^Ph) (H₂^MesPDP^Ph = 2,6-bis(5-mesityl-3-phenyl-1H-pyrrol-2-yl)-pyridine) and its dilithium salt Li₂(^MesPDP^Ph) revealed temperature- and solvent-dependent effects. These molecules, along with the hydrochloric acid adduct [H₃(^MesPDP^Ph)]Cl were found to exhibit short-lived photoluminescence in both tetrahydrofuran and benzene solution. These findings confirm the hypothesis that heavy-atom involvement is crucial for the favorable photophysical properties observed for the Zr(PDP)_{2 …}

Synthesis And Modeling Of Manganese Ferrite Nanoparticles For Magnetic Hyperthermia Applications, Margaret E. Thornton

Theses and Dissertations

Biologically targeted magnetic hyperthermia (MH) is a promising cancer therapeutic that is both non-invasive and has the potential to serve as a single-modality cancer treatment. MH operates through the elevation of temperatures between 40-43 °C to induce apoptosis in malignant tumor cells, while the small size of the magnetic nanoparticles preserves the healthy surrounding tissue. At present, MH is limited by low heating efficiency and heterogenous outcomes, and treatment requires direct-injection of the nanoparticles, excluding deep-tissue and metastatic tumors from the therapy. The most popular candidates for MH are the spinel ferrites iron oxide and manganese iron oxide (MFO). These …

Antiviral Effects Of Metalloshielding: Differential Antiviral Activity Of Polynuclear Platinum And Cobalt Compounds, Mary Zoepfl

Theses and Dissertations

The majority of antiviral drug development has focused on virus-specific discovery targeting discrete steps in the individual life cycles. Although great strides have been made for a number of clinically relevant diseases such as human immunodeficiency virus, influenza virus, and hepatitis B, broad spectrum antivirals do not exist. Broad spectrum antivirals would offer (1) treatment for viruses without specifically-targeted antivirals, (2) treatment for viruses which have developed resistance to their available treatments, and (3) a rapidly deployable treatment option in viral epidemics. Many viruses including human cytomegalovirus (HCMV), HIV, and SARS-CoV-2. rely on heparan sulfate (HS), a highly sulfated glycosaminoglycan …

Characterization Of Landfill Leachate For Enhanced Metal Recovery, Hanna Fulford, Amisha Shah, Inez Hua, Nadezhda Zyaykina, Lori Hoagland, Alejandro Rodriguez Sanchez, Umut Bicim

Discovery Undergraduate Interdisciplinary Research Internship

Landfills contain a trove of valuable materials, such as critical, precious, and rare earth metals, that are integral to the United State’s economy and national security. The leachate that filters through landfills picks up these materials, which allows for the possibility of recovery. For this research, samples will be analyzed from landfills throughout the Midwestern United States to provide a baseline on water quality constituents, elements present, and microbial activity. Preliminary data for this study was acquired by analyzing samples of landfill leachate from a landfill in northern Indiana. pH readings indicate that the leachate is slightly basic. It also …

Synthesis Of Molecular Probes For The Detection Of Toxic Analytes, Rashid Mia

Dissertations

Two different types of molecular probes have been synthesized. The first family of probes is the coumarin class of compounds. These chemodosimters are referred to as Low Molecular Weight Fluorescent probes (LMFP). The other type of molecular probe is a macrocycle known as a pillar[5]arene receptor.

The chemodosimters (2.12a-c and 3.12a) were synthesized in four to five steps. The photophysical properties were extensively studied in various solvent systems (DMSO, CH₃CN, DMF, MeOH, EtOH, Me₂CO, MeCO₂Et, CHCl₃, C₆H₅Me, and C₆H₆). Dimethyl sulfoxide (DMSO) …

Rational Design Of Multifunctional Nanocatalysts For Environmental Remediation And Energy Conversion Technologies, Md Ariful Ahsan

Open Access Theses & Dissertations

The discovery of efficient and sustainable carbon-based nanotechnologies to solve both the scarcity of drinking water and global energy crisis has become a paramount task in the last decades. Owed to the fast population growth and industrialization of the modern society, access to potable water and clean energy technologies is becoming very hard around the globe. Water pollutants have become a serious threat to the environment and ecology because of their toxic nature. Parallelly, the current hydrocarbon-based fuel industries are generating high levels of contamination across the planet, making imperative the development of cleaner energy technologies. In this regard, the …

Exploring The Potential Use Of Porous Silica Nanoparticles In Cest-Mri, Lydia Makotamo

Dissertations and Theses

Magnetic resonance imaging (MRI) is a widely used modality in diagnostics, treatment, and monitoring various conditions due to its ability to generate high-resolution images using non-ionizing radiation. The advent of contrast agents, which generally work by increasing the spin relaxation rate constants of water protons, has led to image enhancement. Despite the usefulness of this class of agents in diagnostic medicine, their inability to provide in-depth functional and anatomical information, coupled with their high detection limits, has led to new agents being explored.

Chemical exchange saturation transfer (CEST) presents an alternative route to generate signals via repetitive saturations transfers between …

Designing Environmentally Responsible And Highly Effective Bioorthogonally Functionalized Chiral Mri Contrast Agents, Karley Breann Maier

Dissertations and Theses

Magnetic resonance imaging (MRI) revolutionized diagnostic imaging and modernized the characterization of numerous diseases. The clinical success of MRI is in large part due to the employment of gadolinium-based contrast agents (GBCAs). Due to sensitivity limitations, GBCAs are indicated at markedly high dosages (~1 g Gd³⁺ per exam). The routine use of such large quantities of gadolinium poses significant health and environmental risks. There are growing concerns over the effects of dechelation of the metal in vivo and the possible effect of resulting gadolinium deposition. Concurrently, there is a rising awareness of gadolinium anomalies borne by GBCAs which undergo …

Synthesis And Characterization Of Pyridine-Based Diimide Ligands And Metal Phosphonate Coordination Polymers, Juan L. Pinedo

Honors Program Theses and Research Projects

Coordination polymers have been a topic of interest because of the large variety of applications these materials have. in particular Metal-Organic Frameworks (MOFs) have been researched due to their porosity and simple synthetic pathways. Structurally a MOF is composed of one or more organic ligands serving as the backbone of the structure. These ligands are complexed with metal ions coordinating into the desired structure. It is this structure that gives way to a variable porosity useful for proton conductivity and material transport. By varying backbone size a framework can be customized for use in specific conditions. This is due not …

Premade Nanoparticle Films For The Synthesis Of Vertically Aligned Carbon Nanotubes, Abdul Hoque, Ahamed Ullah, Beth S. Guiton, Noe T. Alvarez

Chemistry Faculty Publications

Carbon nanotubes (CNTs) offer unique properties that have the potential to address multiple issues in industry and material sciences. Although many synthesis methods have been developed, it remains difficult to control CNT characteristics. Here, with the goal of achieving such control, we report a bottom-up process for CNT synthesis in which monolayers of premade aluminum oxide (Al₂O₃) and iron oxide (Fe₃O₄) nanoparticles were anchored on a flat silicon oxide (SiO₂) substrate. The nanoparticle dispersion and monolayer assembly of the oleic-acid-stabilized Al₂O₃ nanoparticles were achieved using 11-phosphonoundecanoic acid …

Corrosion Prevention On Aluminum Alloy, Andrea Brenner

Symposium of Student Scholars

Aluminum alloy (Al-alloy) is a widely used metal in construction, aerospace, aviation, and other necessary fields due to its lightweight and tweakable properties. However, corrosion is inevitable on metals and alloys, and that causes millions of dollars of revenue loss every year. Therefore, we propose to research fabricating coating to prevent corrosion on Al-alloy. This study uses an iron-based metal-organic framework (MOF) and polyurethane (PU) based composite coating to prevent corrosion on the Al-alloy. The makeup of the composite material is changed by varying the percentage of MOF. In addition, a binder is also used to enhance the homogenization between …