Chemistry Commons^™

Detection Of Salen-Type Tracers For Subterranean Fluid Flow Monitoring Using Surface-Enhanced Raman Spectroscopy, Jenny C. Sanchez

Chemistry and Chemical Biology ETDs

A series of hydrocarbon and aqueous soluble salen-type ligands have been synthesized and characterized by electronic and vibrational spectroscopy. Aqueous soluble salen-type ligands were complexed to a metal and investigated as potential underground fluid flow tracers using Surface-Enhanced Raman Spectroscopy (SERS) as the analytical technique. Vibrational spectra obtained from SERS was shown to have enhanced the spectral signal for these complexes in low concentrations though did not show significant differences between the free ligands and their metal complexes. This research has shown that, with some structural modifications, salen-type ligands can be effective candidates as subterranean fluid flow tracers when SERS …

The Preparation Of Palladium Complexes Of N-Pyrazolylpropanamide Derivatives, Tyler Palombo 5275714

Senior Honors Projects, 2010-2019

The reaction of 3,5-dimethylpyrazolyl-N-isopropylpropanamide (L1) with dichloro(1,5-cyclooctadiene)palladium(II) displaces cyclooctadiene forming Cl₂Pd(L1)₂. This complex has been characterized by NMR and IR spectroscopy, single crystal X-Ray diffraction, and elemental analysis. It is composed of a square planar Pd with trans L1 ligands attached through a pyrazolyl nitrogen and intramolecular hydrogen bonding between the amide and chloride. Similar reactions were carried out with 3,5-dimethylpyrazolylpropanamide (L2), pyrazolyl-N-isopropylpropanamide (L3), 3-(1H-benzotriazol-1-yl)-N,N-dimethylpropanamide (L4), 3-methylpyrazolylpropanamide (L5), 3-(1H-benzotriazol-1-yl)-2-methylpropanamide (L6), and N-pyrazolypropanamide (L7) presumably forming analogous complexes. This formulation for …

Photoelectrochemical Studies On Non-Noble Metal Based Catalysts Towards Tandem Solar Water Splitting, Arun Siddarth Sridhar

Dissertations

Photoelectrochemical (PEC) water splitting makes direct use of solar energy incident on semiconductor photoelectrodes, and it is a convenient, economic option to produce high purity hydrogen at low temperatures. The use of multiple light absorbers can increase overall solar energy utilization and provide a solution to the trade-off between overall band gap and band edge positioning of photoelectrodes specific to solar water oxidation and water reduction. The study of non-noble metal based catalysts for hydrogen evolution reaction (HER) and oxygen evolution reactions (OER) are essential for economic practical commercialization of photo-electrolyzers. This dissertation focuses on the use of a variety …

Photoelectrochemical Investigations On Novel Earth Abundant Solid State Catalysts For Solar Water Oxidation, Nathaniel Branimir Kurtz

Honors Theses

In light of a looming fossil fuel scarcity, many forms of alternative, clean energy production are being researched in order to provide a more sustainable source of energy production for the future. One area of research is on using novel, abundant catalytic materials in conjunction with semiconducting materials to drive the splitting of water in order to produce hydrogen gas, an energy-rich fuel. Currently, efficiency is limited by the energy bottleneck posed by the oxygen evolution reaction (OER) half of water splitting. In this work, cobalt selenide (CoSe) catalyst paired with the semiconductor iron oxide (Fe2O3) has been identified as …

Synthesis Of A Silsesquioxane Based Supramolecular Polymer, Rachel Bianculli

Honors Projects

Research toward smart materials, specifically self-healing polymers, is an expanding topic within the materials science field. These materials rely heavily on dynamic crosslinking that is achieved by inducing different degrees of hydrogen bonding, van der Waals forces, etc. This work, demonstrated by research previously done within the Ostrowski research group, shows how coordination bonds of transition metals have been shown to create light activated, self-healing properties. Work done with these light-activated chromium (III) complexes with a poly(butylyene-co-ethylene) backbone have shown how metal—ligand coordination geometries can tune mechanical properties of the polymeric material. However, these materials suffer from being incredibly soft …

Development Of Rules Of Attraction For Intercalated Guest Molecules Inside Of A Hydrogen Bonded Framework, Matthew Fischer

Dissertations

Supramolecular chemistry has synthesized large and small molecules which host guest molecules for several decades. What started as a way to mimic of enzymes in nature, has exploded into a sea of materials such as porous coordination polymers, low-density metal-organic frameworks, inclusion compounds, and hydrogen bonded frameworks. We previously designed a layered framework consisting of a metal complex with coordinate covalent ligands. These ligands have peripheral carboxylic acid groups which hydrogen bond to organic pillars containing terminal amines. The layered structure is separated by these pillars, which are closed-packed, creating 1-dimensional channels able to co-crystallize molecules. There is interest in …

Steric Effects On The Formation Of Manganese Oxide Clusters And 2-Dimensional Ammonium Formate Architectures, Carl Oberle

Dissertations

It has been demonstrated by the Beatty group that altering the identity of the ortho-substituent of a dianiline counterion affects the assembly and dimensionality of a cadmium-chloride layer from 2-D to 0-D. This work seeks to extend this finding to metal oxide and organic hydrogen-bonded materials. By systematically increasing the ortho­-substituent’s size on the benzoate building block of reported manganese oxide clusters, of formula Mn_xO_y(O₂C-R)_zL_w (where R = Alkyl, L = neutral monodentate ligand), we aim to impact the self-assembly of these materials relative to their parent …

Environmentally Benign Catalysts By Design: Functional Mimics Of Meralloenzymes, Niharika Botcha, Brianna Sullivan, Nirupama Singh

Research Horizons Day Posters

No abstract provided.

From Flasks To Applications: Design And Optimization Of Giant Quantum Dots Using Traditional And Automated Synthetic Methods, Christina J. Hanson

Nanoscience and Microsystems ETDs

Semiconducting nanocrystals, also known as quantum dots (QDs), that emit light with near-unity quantum yield and are extremely photostable are attractive options as down-conversion and direct electricity-to-light materials for a variety of applications including solid-state lighting, display technologies, bio-imaging and optical tracking. Standard QDs with a core/thin shell structure display fluorescence intermittency (blinking) and photobleaching when exposed to prolonged room temperature excitation for single dot measurements, as well as significant reabsorption and energy transfer when densely packed into polymers or at high solution concentrations.

We have developed thick shell “giant” QDs (gQDs), ultra-stable photon sources both at the ensemble and …

Imidazolium Ionic Liquids As Multifunctional Solvents, Ligands, And Reducing Agents For Noble Metal Deposition Onto Well-Defined Heterostructures And The Effect Of Synthetic History On Catalytic Performance, Michael Drake Ballentine

Masters Theses & Specialist Projects

1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([BMIM]Tf2N) was investigated as a multifunctional solvent, ligand, and reducing agent for platinum deposition onto well-defined CdSe@CdS nanorods. Platinum deposition was carried out thermally and photochemically using Pt(acac)2 as the metal precursor. Thermal deposition was investigated in [BMIM]Tf2N with and without addition of a sacrificial reducing agent, and product topology was compared with the products obtained from polyol reduction using 1,2-hexadecanediol, oleic acid, and oleylamine in diphenyl ether. Photochemically induced platinum deposition was carried out at room temperature in [BMIM]Tf2N, and product topology was compared with the photodeposition products obtained from a toluene dispersion. Thermal deposition of platinum …

Versatile Sarcosine Biosensing Schemes Utilizing Layer-By-Layer Construction Of Carbon Nanotube-Chitosan Composite Films, Michael J. Pannell, Elizabeth E. Doll, Najwa Labban, Mulugeta B. Wayu, Julie A. Pollack, Michael C. Leopold

Chemistry Faculty Publications

Layer-by-layer composite films of carbon nanotubes (CNTs) within a chitosan matrix with sarcosine oxidase enzyme and capped with Nafion have been developed and optimized as a versatile 1st generation amperometric sarcosine biosensing platform that operates successfully both as an isolated sarcosine sensor as well as a functional component within a creatinine sensor. Accurate measurement of sarcosine in urine and creatinine in blood may help with early diagnosis of diseases such as prostate cancer and renal failure, respectively. In this study, each material within the film is systematically optimized toward sarcosine sensitivity, including a critical evaluation of different CNTs effect on …

Synthesis Of Dimeric Zinc Complexes For Use As Ring Opening Polymerization Catalysts, Kyle D. Brooks, Arnlold Rheingold, David B. Green, Joe Fritsch

Seaver College Research And Scholarly Achievement Symposium

No abstract provided.

Analysis Of Metallic Components Of Gsr From Various Types Of Ammunition And Firearms Utilizing An Sem-Edx, Jenna A. Campbell

Graduate Student Research Symposium

Gunshot residue (GSR) is a chemical reaction that occurs when a firearm is discharged, which emits a cloud of gases from the barrel of the gun. It consists of both the burned and unburned propellant and primer components. These components are either organic or inorganic in nature, respectively. The organic components are located in the gunpowder part of the bullet, while the inorganic components are located in the primer part of the bullet. The primer consists of lead, barium, and antimony. These elements are considered heavy metals. Additionally, lead, barium, and antimony are the three key elements found in the …

Supercell Crystal Structure Of Na2ga2(Bo3)2, Grace Brown

UNO Student Research and Creative Activity Fair

Na₂Ga₂(BO₃)₂O is an oxyborate with a reported crystal structure in the trigonal space group P1c. The literature states that the three-dimensional structure is created from infinite stacking of parallel [NaGa₂(BO₃)₂] ∞ sheets separated by sodium layers. Our single-crystal X-ray diffraction data requires some modification to this structure. We believe that Na₂Ga₂(BO₃)₂O actually possesses a supercell crystal structure with lower symmetry. The borate anions within the [NaGa₂(BO₃)₂ ] sheets are not parallel to each …

Systematic Size Control In The Synthesis Of Zero-Valent Iron Nanoparticles, Grant C. Bleier

Chemistry and Chemical Biology ETDs

A novel synthetic method for the production of highly magnetic, low size-dispersity nanoparticles through reversible magnetic agglomeration is introduced and studied in detail. Initially, a weakly coordinating surfactant (3-octadecyl-2,4-pentanedione) is employed to produce a wide range of nanoparticle sizes ranging from 8 to 20 nm in diameter. The kinetics faced in these reactions by cheap and widely available iron complex precursors can be avoided in this method with the introduction of thermodynamic control, which occurs in the form of a magnetic precipitation event that essentially halts nanoparticle growth. Utilizing this synthetic method, the length of the alkyl chain on the …

Ruthenium Complexes Of The General Formula [Rucl 2 (Phox) 2 ] As Precatalysts In Propargylic Substitution Reactions, Negar Jourabchian, Kellsie Jurkowski, Eike Bauer

Chemistry & Biochemistry Faculty Works

After activation by chloride abstraction utilizing NaBArF as an activator (BArF = tetrakis(3,5-bis(trifluoromethyl)phenyl)borate), a complex of the general formula [RuCl2 (PHOX)2 ] was utilized as a catalyst in propargylic substitution reactions, where PHOX is a phosphinooxazoline ligand. Oxygen and nitrogen-centered nucleophiles could be employed in the substitution of a propargylic acetate to obtain the corresponding propargylic substitution products in 87% to 9% isolated yields (45 °C, 16 h reaction time, toluene solvent, 1-2 mol% catalyst loading, 1-2 mol% activator).

Synthesis Of Volatile And Thermally Stable Aluminum Hydride Complexes And Their Use In Atomic Layer Deposition Of Metal Thin Films, Kyle Blakeney

Wayne State University Dissertations

The research discussed in this dissertation spans both synthetic inorganic and nanomaterials chemistry. Aluminum hydride complexes have been synthesized and characterized which are highly volatile and thermally stable and their potential as reducing agents for ALD of electropositive metal and metal-containing films was evaluated. A major discovery has been the deposition of aluminum metal films by thermal ALD using an aluminum dihydride complex supported by a simple amido-amine ligand (Chapters 2). Aluminum is the most electropositive element deposited by purely thermal ALD to date and represents a significant breakthrough for this field. This process may have important industrial applications and …

Progress Toward The Synthesis Of Novel Bacterial Topoisomerase Inhibitors Derived From Fluoroquinolones. N-1 Alkyne Derivaties, Sara Biel, Michael Barbachyn

Summer Research

Bacterial resistance continues to be a growing threat throughout the world. In the US alone, 2 million people are infected by, and 23,000 die from antibiotic-resistant bacteria each year. 1 Developing antibiotics to treat infections caused by Gram-negative and Gram-positive bacteria has become the focus of research efforts worldwide. Fluoroquinolones are a large, marketed class of antimicrobial agents that are effective against both types of bacteria. They target DNA Gyrase and Topoisomerase IV, type II topoisomerase enzymes that are involved in DNA replication, specifically negative supercoiling and decatenation, respectively.

As fluoroquinolones have been clinically used since the mid 80’s, their …

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 …

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 …

Surface Modification For The Improvement Of Metal/Organic Semiconductor Interfaces, Jonathan Paul Hopwood

Dissertations

Organic electronics have become much of the forefront of scientific research due to their advantages over tradition electronics as well as their applications in consumer devices, medical devices, and harnessing renewable sources of energy. Despite their appeal, two major obstacles are responsible for poor performance and limited applications. These problems occur at the interface between the two main components of the devices, the organic semiconductor and the metal electrodes. The first, high electrical resistance, is a result of the misalignment between the metal’s free electrons and the organic semiconductor’s conduction band. We seek to capitalize on this misalignment using light-responsive …

Exploring New Synthetic Strategies By Using Novel Manganese Carboxylate Complexes Along With Two Alkoxide Based Ligands, 2-(Hydroxymethyl)-Pyridine And 4,5-Bis(Hydroxymethyl)-2-Methylpyridin-3-Ol In The Area Of Polynuclear Coordination Chemistry, Michael A. Reagan

College of Graduate Studies: Theses & Dissertations

Manganese carboxylate complexes have been well studied in the past, due to their relevance in bioinorganic chemistry and as well as their behavior as nanoscale magnetic materials that is called single-molecule magnets (SMMs). SMMs are special class of magnetic materials in which magnetism is intrinsic to the molecule. Polynuclear manganese clusters often possess high spin ground states as well as large and negative magnetoanisotropy, a combination which leads to an energy barrier for the reversal of the magnetization direction. The paramagnetic nature of manganese at its common oxidation states with an ample number of unpaired electrons often leads to high-nuclearity …

Synthesis And Characterization Of Magnetic Cabides And Oxides Nanomaterials, Hei Man Tsui

Theses and Dissertations

The design and development of nanoparticles is of great interest in the current energy and electronic industry. However, based on the current materials available the production cost can be high with insignificant magnetic and mechanical properties. Specifically, rare-earth magnetic materials composed of neodymium and samarium are known for their high magnetic performance, however, due to the cost of development there is a need to develop a versatile and cost effective material. Alternatively, cobalt carbide nanomaterials have shown to be a promising alternative for rare-earth free magnets as they exhibit comparable properties as hexaferrite magnetic materials. The primary goal of this …

Chemical Reduction Of Polycyclic Aromatic Ligands With Heavy Group 2 Metals, Andrew Robert Uresk

Legacy Theses & Dissertations (2009 - 2024)

The chemistry of the alkaline earth metals has received a renewed interest in the last decades. The lighter Group 2 metal, magnesium, has gathered the most attention, as it is a key component of Grignard reagents, while the heavier metals have been less studied. The early alkaline earth metals are known to exhibit some similarity with both the alkali and lanthanide metals in π-complexation reactions with planar aromatic hydrocarbons (PAHs). However, the products of heavier Group 2 elements such as strontium and barium were found to be more difficult to synthesize and isolate, thus requiring the development of new synthetic …

Synthesis And Characterization Of Mpims : Metallopolymers Of Intrinsic Microporosity, Kelly Walter

Legacy Theses & Dissertations (2009 - 2024)

Polymers of intrinsic microporosity (PIMs) are class of polymers known for high surface areas arising from their contorted and rigid backbone structures. While high surface area compounds are applicable in many fields, simultaneous solubility and conductivity in PIMs is still lacking. In general, the monomeric units that form the backbone, necessary to yield inefficient polymer strand packing and contortion, also break conjugation in the along the polymer backbone and therefore limit conductivity. It has been previously noted that extended conjugation and the addition of metal atoms (along the backbone) increases conductivity. We therefore sought to use a strategy whereby the …

A Family Of Cyclooctatetraenyl Lanthanide(Iii) Chloridebridged Dimers : Synthesis, Characterization, And Magnetic Properties, Joshua Sky Greenough

Legacy Theses & Dissertations (2009 - 2024)

Historically, the 10π-aromatic ligand, cyclooctatetraene (COT), has played a pivotal role

Exploring Heterometallic Beta-Diketonates For The Low Temperature Synthesis Of Energy-Related Oxide And Fluoride Materials, Matthew Christopher Barry

Legacy Theses & Dissertations (2009 - 2024)

In order to circumvent the issues associated with traditional ceramic methods such as

Electrochemical Investigation Of The Kinetics Of Chloride Substitution Upon Reduction Of [Ru(Porphyrin)(No)Cl] Complexes In Thf., Jeremy R. Zink, E G. Abucayon, Anthony R. Ramuglia, Arghavan Fadamin, James E. Eilers, George B. Richter-Addo, Michael J. Shaw

SIUE Faculty Research, Scholarship, and Creative Activity

The electrochemistry of several ruthenium porphyrin nitrosyl chloride complexes [Ru(por)(NO)Cl] have been examined in tetrahydrofuran. The complexes undergo 1-electron irreversible reductions which result in the diffusion-limited substitutions of the chloride ligands for THF. This chloride metathesis is reversible in the presence of added NBu₄Cl, and equilibrium constants and rate constants for chloride loss have been estimated. These parameters correlate with the NO stretching frequencies of the parent complexes, with more electron-donating porphyrin ligands favouring chloride loss from the reduced complexes. The [Ru(por)(NO)(THF)] products of the reductions can be detected by IR, EPR and visible spectroscopies. These species undergo …

Research And Development Of Optically Transparent Join With Low Processing Temperatures, Eric Kevin Muskovin

Masters Theses

The purpose of this study was to investigate durable solar cell cover glass joins produced by diffusion bonding with deep eutectic solvents (DES) and to develop a novel process of joining optically transparent materials at low temperatures. A joined PV cell-glass specimen was characterized using Raman, μ-FTIR, SEM-EDS, and thin-film XRD. DESs were created with malonic acid (MAL) and choline chloride (ChCl) of varying composition factors (CF; CF=MAL/ChCl). Joining borosilicate glass coupons was attempted using DESs with CF = 0.65 and 1 at temperatures between 100-150 °C for 20 hours. Joining the glass coupons failed at all temperatures and oxygen …

Stability Of Bimetallic Clusters In Protein Model Systems, Sean Hartnett

Master’s Theses

Heterobimetallic cofactors are commonly found in proteins and allow them to perform unique chemical processes that would otherwise not be possible. The interactions between these metals allow the protein to accomplish difficult chemical transformations. Previously, the thermodynamic stability of a Fe^II /Mn^II cluster in the dinucleating ligand F-HXTA (5-fluoro-2-hydroxy-1,3-xylene-α,α′-diamine-N,N,N′,N′-tetraacetic acid) has been investigated in our lab as a model of cluster assembly in the proteins ribonucleotide reductase (RNR) and R2-like ligand binding oxidases (R2lox). By measuring equilibrium concentrations of F-HXTA complexes via ¹⁹F-NMR, it was found that the equilibrium for metal exchange between the homobimetallic …