Inorganic Chemistry Commons^™

Selective Catalytic Oxidation Of Organic Sulfides By Iron (Iii) Porphryin Catalysts And Generation Of Iron (Iv)-Oxo Prophyrin Radical Cations, Nawras A. Asiri

Masters Theses & Specialist Projects

Macrocyclic ligand-complexed transition metal-oxo intermediates are the active oxidizing species in a variety of important biological and catalytic oxidation reactions. Many transition metal catalysts have been designed to mimic the predominant oxidation catalysts in nature, namely the cytochrome P450 enzymes. Iron porphyrin complexes have been the center of research as catalysts. In this study 5,10,15,20- tetramesitylporphyrin (H₂TMP) and its corresponding iron complexes Fe^III(X)TMP (X= Cl, ClO₄, ClO₃, NO₃, NO₂, and BrO₃) have been successfully synthesized and fully characterized by UV-vis and NMR spectroscopies. For the catalytic …

Synthesis And Computational Studies Of A New Class Of Lanthanide Niobate Cluster : [Ln4(H2O)8(So4)5(Nbo3)2]+3h2O; Ln= Dy, Tb, Brady D. Garabato

Masters Theses & Specialist Projects

Polyoxoniobates (PONbs) are a small family of highly electron-rich clusters. The development of new solids composed of these clusters have applications in green energy and electronics. However, the high charge environment of PONbs typically requires alkaline synthetic conditions that are unsuitable for introducing other metals and organic molecules, making synthesis of new systems difficult. To date, very few transition metals and organic ligands have been incorporated into these PONb solids, and lanthanide metal inclusion, which generally improves photoconductivity due to longlived f-orbital excitations, has not yet been fully realized. Here, the synthesis of a new class of lanthanide niobate cluster …

Ionic Conductivity In Non-Ionic Compounds, Usha Kranthi Avala

Masters Theses & Specialist Projects

The main objective of this work is to investigate the ionic conductivity of the drugs under certain conditions and also to compare the ionic conductivities of drugs determined by single surface sensors and parallel plate sensors. The ionic conductivity of various materials at their pre-melt and melt states are studied in order to further study a recently discovered phenomenon. Polar solids like Lidocaine, Ketoconazole, Procainamide and Nifedipine were examined in this study. Experimental studies show an increase in ionic conductivity in both pre-melt (20 -30 °C below melting temperature) and melt transition regions. Results of ionic conductivity of both parallel …

X-Ray Crystal Structures Of: [Rh2(N-{2,4,6-Ch3}C6h2)Coch3)4]•2ncc6h4 And Ba1.5[Fe(C10h13n2o7)][Co(Cn)6]•9h2o; Two Crystallographic Challenges, Kenneth K. Kpogo

Electronic Theses and Dissertations

The novel compound, [Rh₂(N-{2,4,6-CH₃}C₆H₂)COCH₃)₄] was synthesized. Crystal structures of [Rh₂(N-{2,4,6-CH₃}C₆H₂)COCH₃)₄]·2NCC₆H₅ and Ba_1.5[Fe(C₁₀H₁₃N₂O₇)][Co(CN)₆]·9H₂O were determined employing a Rigaku Mercury375R/M CCD (XtaLAB mini) diffractometer with graphite monochromated Mo-Kα radiation. For [Rh₂(N-{2,4,6-CH₃}C₆H₂)COCH₃)₄]·2NCC₆H₅, the space group was P-421c(#114) with unit cell dimensions: a =11.0169(14)Å, c =21.499(3)Å, V …

Characterization By Nmr Of Reactants And Products Of Hydrofluoroether Isomers, Cf3(Cf2)3och3 And (Cf3)2c(F)Cf2och3, Reacting With Isopropyl Alcohol, Howard Knachel, Vladimir Benin, William E. Moddeman, Janine C. Birkbeck, Thomas A. Kestner, Tayna L. Young

Chemistry Faculty Publications

The 3M Company product Novec™ 71IPA DL, a mixture of methoxyperfluorobutane, methoxyperfluoroisobutane and 4.5 wt.% isopropyl alcohol, has been found to be very stable at ambient temperature, producing fluoride at the rate of ~1 ppm/year. Our earlier kinetic and theoretical studies have identified the reaction mechanism. This paper identifies the ¹H and ¹⁹F NMR chemical shifts, multiplicities, and coupling constants of reactants and the major products that result from aging the mixture in sealed Pyrex NMR tubes for periods up to 1.8 years at temperatures from 26 °C to 102 °C. Chemical shifts and coupling constants of fluorine …

A, Catalysis Of Co-Prox By Water-Soluble Rhodium Fluorinated Porphyrins. B, Studies Toward Fluorination Of Electron Rich Aromatics By Nucleophilic Fluoride, Shri Harsha Uppaluri

Department of Chemistry: Dissertations, Theses, and Student Research

The rhodium(III) derivative of a water soluble, heavily fluorinated porphyrin is shown to catalyze the low temperature, low pressure selective oxidation of carbon monoxide in hydrogen gas streams for use in fuel cell applications. The catalytic activity is a direct result of the removal of electron density from the metal center. Selectivity for CO oxidation is a direct consequence of fluorination of the porphyrin periphery, since these substituents enhance the rate of the reaction and prevent the formation of Rh(II)-Rh(II) dimmers. Significantly, the dramatic increase in rhodium hydride acidity caused by fluorination precludes hydrogen activation and generation, thereby permitting preferential …

Surface Tethered Pamam Dendrimers On Controlled Pore Glass As Color Release Sensors For Phosphates, Chang Liu

Master's Theses

Poly(amidoamine) dendrimer (PAMAM) are highly branched macromolecules with reactive amine groups in their interior and exterior. PAMAM dendrimers were attached to controlled pore glass (CPG) surfaces in order to create new functionalized surfaces and used as platforms for UV-vis and fluorescent sensing of phosphate substrates via indicator displacement assays (IDA).

CPG surfaces were first modified with different sized PAMAM dendrimers (generation 3.0, 4.0, and 5.0), then reacted with two strong metal-chelators: aminofunctionalized terpyridine (synthesized from 2,2’:6’,2’’-terpyridine) and Nα-Nα-bis(carboxymethyl)-L-lysine (Lys-NTA). First of all, Cu(II) metal ion binding capacities were measured on the surfaces. Second, two terminal group density tests, amine assay …

Nanomaterials For Biological Applications: Drug Delivery And Bio-Sensing, Hui Ma

LSU New Orleans Theses and Dissertations

The idea of utilizing nanomaterials in bio-related applications has been extensively practiced during the recent decades. Magnetic nanoparticles (MPs), especially superparamagnetic iron oxide nanoparticles have been demonstrated as promising candidates for biomedicine. A protective coating process with biocompatible materials is commonly performed on MPs to further enhance their colloidal and chemical stability in the physiological environment. Mesoporous hollow silica is another class of important nanomaterials that are extensively studied in drug delivery area for their ability to carry significant amount of guest molecules and release in a controlled manner.

In this study, different synthetic approaches that are able to produce …

Enhanced Structural Support Of Metal Sites As Nodes In Metal-Organic Frameworks Compared To Metal Complexes, Sanjit Das

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

Crystalline porous materials have gained long-standing interest for their application in gas storage, separation and catalysis. These materials have been useful for domestic, scientific and industrial purposes for many decades. Zeolites are a well known example of such materials.

Metal-organic frameworks are a new class of crystalline porous materials. They have many advantages over the more widely known zeolites. Though metal-organic frameworks are relatively new, their basic structure, known as the secondary building unit, very closely resembles the structure of metal complexes. Such metal complexes have been characterized in chemistry for more than a century.

Chemical catalysis is a process …

The Investigation Of Protonation Of [Mo2(Nto)2(S2p(Oet)2)2(So)(Sbn)(O2cme)]., Adria Schwarber

College of Arts & Sciences Senior Theses

No abstract provided.

Interaction Between Lubricants Containing Phosphate Ester Additives And Stainless Steels, David W. Johnson, Matthew Bachus, John E. Hils

Chemistry Faculty Publications

One way to improve fuel efficiency in today’s jet aircraft engines is to create an environment for higher operating temperatures and speeds. New and improved lubricants and bearing materials must be developed to remain stable in these elevated operating temperatures. Three lubricants, with varying amounts of tricresyl phosphate added as an anti-wear/extreme pressure additive were tested on two different stainless steels at varying temperatures ranging from 300 °C to 350 °C in vacuum. Significant decomposition of the lubricant base-stocks and the phosphate ester additive did occur in most of the trials resulting in the formation of carboxylic acids and phenols. …

An Investigation Of The Electronic Coupling In Some Dimeric Ruthenium (Ii) Polypyridine Complexes, Roland Ngebichie Njabon

Graduate Theses and Dissertations

A detailed understanding of respiration at the molecular level requires an understanding of the many electron transfer steps involved in the process. These electron transfer processes are extremely fast and are impossible to measure by simple rapid mixing techniques. In order to get around this problem, scientists have used laser flash photolysis. This technique relies on the fact that under proper conditions, a reactant can be generated by a very short laser pulse. Once generated, the course of the reaction can be monitored by various techniques capable of very rapid time response. Many applications of this methodology rely on the …

On Chlorine Salts: Their Detection, Stability And Implications For Water On Mars And Europa, Jennifer Hanley

Graduate Theses and Dissertations

Chlorine salts (e.g. chlorides, chlorates and perchlorates) are an important factor in the stability of water on the surfaces of planetary bodies. Here we have shown that perchlorate and chlorate salts will lower the freezing point of water, allowing it to be liquid down to ~204 K. These salts will also slow down the evaporation rate, extending the lifetime of the liquid water solution. Chlorine salts have been detected on Mars, which has significant implications for the stability of water and hence its habitability. To study their effects on the stability of water on planetary surfaces, we need to first …

New Effects Of Aging And Lattice Intercalation On Surface Properties Of Titanate Nanobelts, Roger Williams

Graduate Theses and Dissertations

Titanate nanobelts (NBs) have structural characteristics beyond that of clays. Due to a negatively charged lattice matrix of edge-shared TiO6-octahedra, the location of intercalated cations within the interlayer space may dictate the charge-conductions. This environment may in turn govern the lattice-framework's stability and surface properties, based upon our preliminary

data.

On that basis, these nanomaterials have been found in our lab to possess superb biological compatibility that is closely related to the types of the intercalated cations. In addition, a prolonged agitation was proven to enable us to manipulate the titanate NBs' length. In a parallel study, a ripening was …

Incorporating Catalysis In Inorganic Chemistry 1 Lecture And Laboratory At Onu, Bradley M. Wile

Chemistry and Biochemistry Faculty Scholarship

No abstract provided.

Multiscale Modeling Of Enzyme-Catalyzed Methanol Production By Particulate Methane Monooxygenase, Katherine K. Bearden

Doctoral Dissertations

In this work, the conversion of methane to methanol by the particulate Methane Monooxygenase (pMMO) enzyme is investigated using a multi-scale modeling approach. This enzyme participates in carbon cycling and aids in the removal of harmful atmospheric methane, converting it to methanol. The interaction between pMMO and a neighboring enzyme that is present in the same organism is studied, and the unknown pMMO active site is elucidated and tested for methane oxidation towards the production of methanol.

Fundamental knowledge of pMMO's mechanism is not fully understood. Understanding how this enzyme works in nature will provide information towards designing efficient synthetic …

Nanoparticle Film Assemblies As Platforms For Electrochemical Biosensing – Factors Affecting Amperometric Signal Enhancement Of Hydrogen Peroxide, Adrienne R. Schmidt, Natalie D. T. Nguyen, Michael C. Leopold

Chemistry Faculty Publications

Factors affecting the enhanced amperometric signal observed at electrodes modified with polyelectrolyte–gold nanoparticle (Au-NP) composite films, which are potential interfaces for first-generation biosensors, were systematically investigated and optimized for hydrogen peroxide (H2O2) detection. Polyelectrolyte multilayer films embedded with citrate-stabilized gold nanoparticles exhibited high sensitivity toward the oxidation of H2O2. From this Au-NP film assembly, the importance of Au-NP ligand protection, film permeability, the density of Au-NPs within the film, and electronic coupling between Au-NPs (interparticle) and between the film and the electrode (interfacial) were evaluated. Using alternative Au-NPs, including those stabilized with thiols, polymers, and bulky ligands, suggests that the …

Monolayer-Protected Nanoparticle Doped Xerogels As Functional Components Of Amperometric Glucose Biosensors, Michael Hartley Freeman, Jackson R. Hall, Michael C. Leopold

Chemistry Faculty Publications

First-generation amperometric glucose biosensors incorporating alkanethiolate-protected gold nanoparticles, monolayer protected clusters (MPCs), within a xerogel matrix are investigated as model systems for nanomaterial-assisted electrochemical sensing strategies. The xerogel biosensors are comprised of platinum electrodes modified with composite films of (3-mercaptopropyl)trimethoxy silane xerogel embedded with glucose oxidase enzyme, doped with Au225(C6)75 MPCs, and coated with an outer polyurethane layer. Electrochemistry and scanning/transmission electron microscopy, including cross-sectional TEM, show sensor construction, humidity effects on xerogel structure, and successful incorporation of MPCs. Analytical performance of the biosensor scheme with and without MPC doping of the xerogel is determined from direct glucose injection during …

Synthesis And Characterization Of Metal Complexes Containing Tetrazolate, Poly(Tetrazolyl)Borate, And Poly(Azolyl)Aluminate Ligands As High Energy Density Materials, Christopher James Snyder

Wayne State University Dissertations

A series of heavy alkaline earth metal tetrazolate complexes has been synthesized that contain metal ions saturated by aqua ligands. Tetrazolates with small ring-core carbon substituents favor formation of two dimensional polymers with u3-coordination of the tetrazolate to the metal centers. Tetrazolates with bulkier groups block coordination to the 1- and 4-nitrogen atoms, resulting in monomer formation. The first example of a trihydro(tetrazolyl)borate was prepared, and its bonding is heavily influenced by the basic BH3 moiety. 18-Crown-6 adducts of dihydrobis(tetrazolyl)borate complexes have been prepared that contain B-N bonding to the 2-nitrogen atoms, due to bulky ring-core atom substituents. A series …

Synthesis And Characterization Of Transition Metal Arsenide Nanocrystals And The Metastability And Magneto-Structural Phase Transition Behavior Of Mnas Nanocrystals, Yanhua Zhang

Wayne State University Dissertations

This dissertation study focuses on (1) probing the magneto-structural phase transformation in nanoscale MnAs; (2) evaluation of the size-dependent phase stability of type-B MnAs (prepared by rapid injection); and (3) developing a general synthetic method for transition metal arsenide nanoparticles.

Discrete MnAs nanoparticles that adopt different structures at room temperature (type-A, α-structure and type-B, β-structure) have been prepared by the solution-phase arrested precipitation method. Atomic pair distribution and Rietveld refinement were employed on synchrotron data to explore the structural transitions of the bulk and nanoparticle samples, and these results were compared to AC magnetic susceptibility measurements of the samples. The …