Physical Sciences and Mathematics Commons^™

Allosteric Tuning Of Ruthenium 2,2’-Bipyridyl Luminescent Sensor Systems, Daqing Gan

Masters Theses

A series of new ruthenium bipyridyl crown supramolecular sensor systems containing two binding sites were synthesized. The crystal structure and photophysical properties of the developed sensor systems were thoroughly studied using x-ray, nuclear magnetic resonance and photoscopy methods. It turned out that the chelation of transition metal on the remote sites of the bipyridyl crown ligands greatly reduced the reactivity of the crown cavity. It is believed that the chelation of transition metal on the nitrogen atoms forces the bipyridyl function towards coplanarity and restricts the conformational freedom of the crown ring. The conformational rigidity in turn influences the binding …

Redox Studies On The Anti-Rheumatoid Arthritis Gold Drugs: Auranofin And Solganol, Ahmed A. Mohamed

Electronic Theses and Dissertations

The oxidative behavior of Auranofin, 2,3,4,6-tetra-O-acetyl-1-thio-β-D-glucopyranosato-S(triethylphosphine)gold(I), was investigated by using cyclic voltammetry (CV) in 0.1 M Bu₄NBF₄/CH₂Cl₂ and 0.1 M Bu₄NPF₆/CH₂Cl₂ solutions using Pt working and auxiliary electrodes and a Ag/AgCl reference. CV studies at scan rates from 50-2,000mVs^-1 and Auranofin concentrations between 1 and 4mM, show two irreversible oxidation processes occurring at +1.1 V and +1.6 V vs. Ag/AgCl. Treatment of Auranofrn with the one electron oxidizing agent [Cp₂Fe]PF₆ gave a μ-thiolato digold cluster, [(Et₃PAu)₂(μ-SR)]₂^{2+ …}

Dendritic Polymers As Bonded Stationary Phases In Capillary Electrochromatography, Chiayu Helen Chao

Seton Hall University Dissertations and Theses (ETDs)

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Copper Complexation And Speciation In The Western South And Equatorial Atlantic Ocean, John A. Consolvo

Chemistry & Biochemistry Theses & Dissertations

Presented here are the first data on copper complexation and speciation in the South Atlantic Ocean. Samples were collected at six vertical profile stations and along the surface (1m) transect during the 1996 IOC Baseline Contaminant Survey. Copper complexation measurements were made for the surface transect (1m) samples and three of the six vertical profile stations (1m - ~500m) using differential pulse anodic stripping voltammetry (DPASV) with a thin mercury film, rotating glassy carbon disk electrode (TMFRGCDE).

A strong organic copper complexing ligand (L₁; log K' _cuL1/cu2+ > 11. 8 ± 0 .4) was detected in 57% of all …

Fourier Transform Raman Spectroscopy For Process Control In The Petroleum Industry, Kent Lawson Wise

Chemistry & Biochemistry Theses & Dissertations

As early as 1950, Raman spectroscopy was proposed as a method to determine aromatics and olefins in hydrocarbon mixtures. Until recently, extensive use of Raman spectroscopy in the characterization of hydrocarbons has not been practical due to several limitations. One early limitation to Raman analysis was the absence of a high intensity and stable excitation source. This problem has been overcome with the advent of lasers. Another limitation was the presence of fluorescence in hydrocarbon fuels when excited by visible lasers. However, the development of Fourier-transform Raman spectrometers now allows Raman spectra to be collected using near-IR lasers (e.g …

The Development Of A Lutetium Recovery Plant, Peter Michael Smith

Doctoral Dissertations

This research project focused on the scale-up of an industrial facility for the continuous counter-current solvent extraction (CCCSX) separation of lutetium. CCCSX involves a multistage apparatus for the mixing in each stage of two immiscible liquid phases to transfer an analyte from one phase to the other. The two phases continuously flow in opposite directions in a CCCSX system. In this research, aqueous lutetium solutions, obtained from the acid leaching of lutetium oxyorthosilicate, were mixed with kerosene solutions of phosphorus based metal extractants (e.g. mono-2-ethylhexyl-(2- ethylhexyl) phosphonic acid, MEHEHP). This system extracted the lutetium from the aqueous phase, transferring the …

Photophysical Study Of Linked 1,4,7-Triazacyclonane Cr (Iii) Complexes, Weizhen Tu

Masters Theses

A series of mono and bimetallic Cr(III) complexes based on the 1,4,7- triazacyclonoane(TACN) were prepared. Complexes of the Cr(TACN)X₃ , and Cr₂(DTNE)X₆ demonstrated marked difference of photophysical properties on the nature of X. In cases where X is more easily oxidized, enhanced extinction coefficient in the ⁴A₂ ➔ ²T, absorption and larger quantum yield of emission at 77K were observed in the dimer complexes. Shorter lifetime and enhanced decay rate were also found in the dimer complexes suggests that there might exists weak coupling behavior between the two Cr(III) metal cents in the …

Reaction Of Caffeic Acid With Amino Acids, Yonggang Wang

Masters Theses

The reaction of caffeic acid with tryptophan was studied as a model for the reaction of caffeic acid with amino acids in the aquatic environment. Although the autoxidation reaction of caffeic acid in aqueous solution with subsequent dimerization had been previously studied, it was examined as well for comparison purposes. The present studies demonstrate that oxidized caffeic acid would react with tryptophan. The reaction, like the dimerization reaction, was catalyzed by the presence of iron(III) ions at low pH ( <4) and by hydroxide ions at high pH (10). The reaction of caffeic acid with itself yielded six products, four of which were identified by mass spectroscopy as dimers, with the other two being trimers. The reaction of caffeic acid with tryptophan yielded three product peaks. Two of the product peaks had similar retention times to the dimers from the self-reaction of caffeic acid; the third was a new product resulting from the reaction of caffeic acid with the tryptophan.

A mechanism for the reaction of caffeic acid with tryptophan has been proposed. This mechanism was based on the analysis …

Cyclodextrin Inclusion Complexes Of Betamethasone-Related Steroids Studied Using Hplc, Keith Gerald Flood

Seton Hall University Dissertations and Theses (ETDs)

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Investigations On The Use Of Ion Mobility Spectrometry For Clinical Chemistry Applications, Henri Parson Patten

Theses and Dissertations in Biomedical Sciences

The major objective of this research is to examine ion mobility spectrometry as a rapid screening tool for specific application to clinical chemistry research and laboratory use. Methodology was developed for target analytes representing several classes of physiologically active substances, including anesthetics, illicit drugs, and their metabolites. The IMS characteristics of animal tissues and other compounds such as amino acids and proteins were determined. Quality assurance and control procedures were developed for specific quality data objectives. Criteria were established relating to use of IMS for assessing the precision and accuracy of data, qualitative screening, and semi-quantitative analyses.

It was found …

Forensic Applications Of Capillary Electrophoresis, Jennifer A. Jakubowski

Honors Theses

The separation by capillary zone electrophoresis (CZE) of the chiral narcotic propoxyphene is the goal of this work. A three-way collaboration between our research group, Professor lsiah Warner (LSU), and the New York State Forensic Investigation Center is underway, with the goal of separating controlled substances and developing techniques that the Forensic Center can apply in it& investigations. Earlier studies by Warner's group have shown that using polymerized N-undecylenyl-L-amino acid and peptide derivatives as pseudo-stationary phases in CZE has resulted in the separation of chiral molecules. Our separations were attempted by combining the drug samples with polymerized N-undecylenyl-L-amino acid and …

Stereoselection In The Preparation Of Alpha-Oxy-Beta-Amino Esters : Revealing The Mechanism, Richard James Fox

Honors Theses

Due to their significant pharmaceutical applications, the development of efficient, stereoselective synthetic routes for the preparation of α-substituted-β-amino esters has become increasingly important. We demonstrated that the titanium enolates (47) of a.alkoxy acetate esters (48) add cleanly to imines (49), and predominately afford the anti diastereomer of the a.-oxy-f3-amino ester product (50). Furthermore, by altering the electronic properties of the ether oxygen, sterics of the ester and temperature conditions, we changed the anti:syn product ratio. We rationalized the origin of these effects, and proposed a mechanism of imine addition.

Diastereoselection In Titanium Enolate Addition To Aldmines, Julia Leigh Barkin

Honors Theses

A mild and versatile synthesis of a-oxy-6-amino esters has been performed by condensation of the chlorotitanium enolates of methyl methoxyacetate with aldimines. The imine-aldol addition occurs in excellent yields without Lewis acid activation of the imine. All aryl imines examined show good to excellent diastereoselection for the anti isomers.

Fluorescence Studies Of Tris (2,2'-Bipyridine) Ruthenium (Ii) In Thin Clay Films, Samuel James Salamone

Honors Theses

Because of their rich intercalation chemistry and ability to enhance the thermal stability of the included guest, layered silicate clays are excellent hosts for the fabrication of organic/inorganic nanocomposites. Composites of hectorite and tris(2, 2' -bipyridine) ruthenium(U), Ru(bpy), 3 2+, have attracted attention owing to their potential applications as glucose and oxygen based chemical sensors. Previous studies on the fluorescence behavior of Ru(bpy)3 2+ complexes in aqueous colloidal clay suspensions have shown enhanced emission traces. We report here the first study of the fluorescence responses of Ru(bpy) 3 2+ exchanged thin clay films. Variation of guest concentration and exposure time …

Structures, Intermolecular Rotation Barriers, And Thermodynamic Properties Of Chlorinated Methanols And Chlorinated Methyl Hydroperoxides, Hongyan Sun

Theses

Thermochemical property data on chlorinated methanols and methyl hydroperoxides are important in oxidation, combustion and atmospheric photochemistry of chlorocarbons, Enthalpy, entropy, and heat capacities are determined for three chlorinated methanols and three chlorinated methyl hydroperoxides using density frnctional, B3LYP/6-31G(d,p), B3LYP/6-311+G(3df,2p), ab initio QCISD(T)/6-31G(d,p) and the composite CBSQ/B3LYP/6-31G(d,p) calculation methods. Molecular structures and vibration frequencies are determined at the B3LYP/6-31G(d,p) density functional calculation level. Vibration frequencies are scaled for zero point energies and for thermal corrections. ΔH°_{f 298} are determined at each calculation level using the ΔH_rxn,298 with known enthalpies of other reactants and products in each of five …

Thermochemical Properties Of Methyl And Chloro-Methyl Hyplochlorites And Ethers And Reaction Of Methyl Radical With Clo, Dawoon Jung

Theses

Hypochlorites are formed from reactions of chlorine monoxide (ClO) addition to unsaturates and association with radicals. ClO is a prevalent and an important species in chemistry of the atmosphere and in combustion systems where chlorine is present. Thermochemical property data on these oxy-chlorocarbon species are important to understanding the reaction pathways and kinetics in these environments. Enthalpy, ΔH_f°_298, entropy, S°_298, and heat capacities, C_p(T) from 300 to 1500 K are determined for methyl hypochlorite and three chloro-methyl hypochlorites and formaldehyde-C1 atomcomplex radicals (CH₂O--Cl, CHClO--CI, CCI₂O--Cl) by density functional, and ab …

Determination Of The Wavelength Dependence On The Metal Catalyzed Degradation Of The Herbicide Atrazine, Timothy Bertram

Honors Theses

Since the advent of modern herbicide use in the early twentieth century, researchers have been plagued with the obvious problem of herbicide disposal. Most herbicides are specifically designed to resist natural degradation processes so that they can remain effective in the field for a substantial amount of time. In addition, they are also made water soluble so that they can be easily applied to crops. Finally, they are specifically produced to kill undesirable plant species in the quickest and often crudest fashions. Due to these specific properties herbicides pose a general threat to other organisms living in the same geographic …

Phage Therapy : An Alternative To Antibiotics, Maria A. Appeaning

Electronic Dissertations and Theses

Bacteria resistant to most or all available antibiotics are causing increasingly serious problems and raising widespread fears of returning to a pre-antibiotic era of untreatable infections and epidemics. Despite intensive work by drug companies, no new classes of antibiotics have been found in the last 30 years . There are hopes that the newfound ability to sequence entire microbial genomes and to determine the molecular bases of pathogenicity will open new avenues for treating infectious disease, but other approaches are also being sought with increasing fervor. One result is a renewed interest in the possibilities of bacteriophage (phage) therapy - …

Retention Of Ionizable Compounds In Hplc, Rosario Lobrutto

Seton Hall University Dissertations and Theses (ETDs)

No abstract provided.

Fundamental Capillary Electrophoresis: An Evaluation Of Electrokinetic Sampling, Cindy Ann Mleziva Blake

Seton Hall University Dissertations and Theses (ETDs)

Capillary electrophoresis has become a powerful separation technique in fields of biochemical separations, inorganic ions, and chiral separations. The technique has experienced exponential growth since the historic publication of Zone Electrophoresis in Open-Tubular Glass Capillaries by Lukacs and Jorgenson in 1981. However, the use of capillary electrophoresis as a primary research analysis tool still remains to be seen in many pharmaceutical laboratories. One of the main reasons for this is that it remains difficult to validate CE methods using the criteria of quantitation and accuracy posed by the current government regulating agencies, as developed for high performance liquid chromatography and …

Studies On The Roles Of Atp In Nitrogenase Catalysis, Wei Wu

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

Nitrogenase is the enzyme that catalyzes the reduction of nitrogen to ammonia in a reaction requiring MgATP hydrolysis. Two component proteins of nitrogenase are the iron protein (Fe protein) and the molybdenum-iron protein (MoFe protein).

Nitrogenase contains two nucleotide binding sites. During catalysis, the Fe protein binds two MgATP first. The conformational changes induced upon MgATP binding allow the Fe protein to associate with the MoFe protein. After the formation of the Fe protein-MoFe protein complex, a single electron is transferred from the Fe protein to the MoFe protein, an event that is coupled to MgATP hydrolysis in the Fe …

Rotational Structure Of Extremely Floppy Van Der Waals Complexes: Adiabatic Separation Of Angular And Radial Motion, P. Daniel Ward

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

The adiabatic or Born-Oppenheimer approximation is often used in molecular calculations to simplify the solution to the Schrödinger equation. The basis of the approximation is the large difference in the relative motions of the nuclei and electrons in the molecule—the electrons are able to respond almost instantly to the movements of the nuclei. Thus, the nuclei may be regarded as being fixed in a certain position and the Schrödinger equation can then be solved using the potential obtained by solving the electronic problem at fixed nuclear configuration.

A similar argument can be used to decouple the angular and radial motions …

Photodegradation Of Pcbs In Natural Waters, Adriana R. Nicolaescu

Masters Theses

PCBs are widely distributed in the environment and they are biologically refractory and toxic compounds. There is great interest in understanding their fate in the environment, and also for finding safe and effective degradation methods.

This study is concerned with the photodegradation of four PCB congeners: PCB 5, PCB 18, PCB 77, PCB 128 in natural waters. Natural waters contain humic substances which can greatly influence the environmental fate of the PCBs. The different degradation of the four congeners was studied in standardized systems and in humic acid or nitrate solutions, under environmental conditions. DMDE and Methoxyclor (whose environmental half-lifetimes …

Design, Synthesis, And Evaluation Of A Novel Serine Protease Inhibitor Based On Monocyclic Β-Lactams, Ian M. Paquette

All Theses And Dissertations

Serine proteases are a large family of proteolytic enzymes which utilize a serine residue as a reactive nucleophile in the active site. Some of the more common serine proteases are chymotrypsin, trypsin, thrombin, human leukocyte elastase (HLE), human cathepsin G, and human cytomegalovirus protease (HCMV protease). Unregulated serine protease activity has been implicated in several common ailments, including rheumatoid arthritis, emphysema, pancreatitis, atherosclerosis, cystic fibrosis, and Alzheimer’s disease. Since serine proteases are responsible for the onset of such a wide range of diseases, there is an equivalent need for a large library of synthetic serine protease inhibitors to selectively counteract …

In Situ Treatment Of Chlorinated Ethene-Contaminated Groundwater Using Horizontal Flow Treatment Wells, Derek R. Ferland

Theses and Dissertations

The limitations of conventional containment technologies for groundwater contaminated with chlorinated solvents have motivated development of innovative technologies to achieve national groundwater remediation objectives. One inn9vative technology that is currently under development involves metal reductants or catalysts to chemically destroy the dissolved chlorinated solvent. Models are important tools that can be used to help transition this technology to the field. Model studies can be used to gain understanding about the technology, help determine when the prospective technology might work for a given site, and design full-scale field applications.

Modeling Chlorinated Ethene Removal In Constructed Wetlands: A System Dynamics Approach, Colby D. Hoefar

Theses and Dissertations

The purpose of this study is to gain understanding of the dynamics of the processes that degrade Perchloroethene (PCE) to ethylene, or carbon dioxide (CO₂), within the confines of a constructed wetland. A system dynamics approach will be used. This model is focused on identifying and optimizing the naturally occurring processes in stratified wetland sediment that reduce mass, toxicity, mobility, volume or concentration of contaminants in groundwater. Contaminant fate and transport within a wetland system is extremely complex and the mechanisms that drive wetland behavior are dynamic. Confidence in the model was built through verification and testing. Reasonable …

Chromate Dissociation From Primer Paint In Simulated Lung Fluid, Tiffany J. R. Morgan

Theses and Dissertations

OSHA has proposed a new strontium chromate exposure standard that would potentially cause Air Force paint facilities to be in violation of the proposed standard if adopted. This proposed reduction make the continued use of chromate containing primer paints very difficult. There is currently no acceptable replacements for chromate containing primer paints on AF aircraft. This study suggests that paint particles with chromate bound in primer paint may be unavailable for bodily absorption if inhaled and a reduced standard for painting applications may be unnecessary. Primer paint overspray was collected into simulated lung fluid (SLF) and allowed 6 hr, 24 …

Cisplatin Interstrand Cross-Linking Of Defined Sequence Nucleosomal Dna, Erin Elizabeth Wilkes

Honors Theses

DNA interstrand cross-linking agents have been recognized for many years to be powerful antitumor chemotherapeutics. While the interactions between free DNA and many anticancer drugs have been explored extensively, there is less infonnation available about these interactions with nucleosomal DNA. Nitrogen mustards have been reported to exhibit relatively similar cross-linking sites and efficiencies of binding in free and nucleosomal DNA, but mitomycin C exhibits markedly reduced cross-linking near the center of nucleosomal DNA. This current study focuses on cisplatin interstrand cross-linking of the 154 base pair 55 rRNA gene fragment of Xenopus borealis reconstituted with histones from chicken erythrocytes. The …

A Computational Approach To Determining Stability Constants For Transition Metal Ion Complexes, Jason St. Clair

Honors Theses

The complexation of metal ions in natural waters plays a critical role in defining the metal's biogeochemistry, Numerous investigators have used various experimental techniques to measure complexation constants in the laboratory, but many constants are still poorly undefined or have yet to be investigated due to the difficulty of some of the experiments. A computational approach to obtaining these constants for complexes of Fe(lII), Fe(D), Cr(lli), Cu(lI), Zn(II), and Cd(II) was explored with varying degrees of success. Calculated Gibbs Free Energies were compared to experimental stability constants. Calculations were performed using Spartan's DFT package at the pEP level and with …

Friction Of (110) Diamond In The Presence Of Small Hydrocarbon Molecule, Catherine Manning

Honors Theses

Molecular dynamic simulations have been used to explore the friction between two (110) diamond surfaces in sliding contact. In general, when a third-body hydrocarbon molecule is placed between two computer generated diamond surfaces in sliding contact, the result is a reduction of friction as the load iH increased compared to the same surfaces in the absence of third-body molecules. The size, shape, and alignment of the third-body hydrocarbon molecules play an essential role in the reduction of friction. Results for a system with ethane presented as a third-body molecule will be compared to previous theoretical studies as well as existing …