Physical Sciences and Mathematics Commons^™

Transition Metals As Tools To Probe The Electronic Properties Of Porphyrinoids, Jillian Worlinsky

Chemistry Education Materials

This thesis describes in a number of separate chapters a range of studies that measure the variation of specific physical properties with structural modification of the macrocycles, with a particular focus also on using their coordinated metals as probes. Specifically, the transition metal ions are used as tools for interrogation of the electronic properties of porphyrins and pyrrole-modified porphyrins. With the aim of better understanding the electronic and structural factors that govern the optical responses, axial binding strengths, fragmentation patterns and carbonyl stretching frequencies of meso-tetraarylporphyrins, a rational design of pyrrole-modified metalloporphyrins with designed optical properties is derived.

Preparation Of Organofluorine Compounds: Exploring Mono-, Di-, And Tri-Fluorination, Diandra M. Rudzinski

Master's Theses

Organofluorine compounds exhibit biological activity and have advantageous properties for drug design. Natural occurring fluorinated molecules are rare, demanding new synthetic methods for their preparation. A novel route to access trifluoromethyl ketones from Weinreb amide precursors is discussed. This is the first documented method for the use of the Ruppert-Prakash reagent, (trifluoromethyl)trimethylsilane, for the production of trifluoromethyl ketones from amide starting materials. This method is tolerant of aryl and alkyl substrates exhibited by their moderate to excellent yields. A discussion of the unusual reactivity of these amides, their selectivity for mono-trifluoromethylation, and other mono-, and di-fluorination attempts are reported.

Ultra-Stable Protein-Polymer Bioconjugates, Kyle S. Cole

Master's Theses

No abstract provided.

Preparation Of Nitrogen-Containing Heterocycles Via Cyclization Of Pyridine-Tethered Organolithiums, Elizabeth Archer

Master's Theses

No abstract provided.

Design And Synthesis Of Fluorescence Turn-On Probes For Iron, Randy K. Jackson

Master's Theses

No abstract provided.

Synthesis Of Half-Loaded Nitroimidazole Indocyanine Green Dyes Attached To Carbon Nanotubes, Courtney L. Stanford

Master's Theses

Indocyanine green dye is the only FDA approved NIR fluorescent dye that can be used in humans. 2-Nitroimidazoles are very effective radiosensitizers, have low cytotoxicity, and target hypoxic tissue. By coupling the two together, hypoxic tumors can be targeted and imaged. Previous work has been done to couple 2-nitroimidazole to both sides of the indocyanine green dye. This work focuses on expanding that concept to couple 2-nitroimidazole to only one side of the dye, thus allowing for the other end to be available to couple to another compound, generating a half loaded 2-nitroimidazole indocyanine green dye. In theory, this half-loaded …

Fluorescence Tagging Of Marine Low Molecular Weight Carboxylic Acids, Brian C. Gismervik

Master's Theses

This thesis aims at the evaluation of the best amide bonding strategy that places a fluorescence aminomethyl coumarin tag onto a LMW organic acid in aqueous solution. A three-stage study was conducted. First, a suitable aminomethyl coumarin fluorophore was synthesized. Second, a library of acid-derivatized standards was synthesized for use in optimizing the anticipated HPLC separation of a mixture of LMW acids expected to be found in marine samples. Third, the aforementioned amide coupling strategies were screened to identify the most applicable method for our reaction conditions to the tagging of LMW organic acids in a large number of field …

Mechanistic Studies And Optimization Of Microwave-Assisted Palladium-Catalyzed Carbon-Carbon Bond Forming Reactions And An Academic Prospective On “Quality By Design”, Neha K. Grewal

Honors Scholar Theses

This compilation of work includes four aspects: (1) an academic review on the significance and implementation of Quality by Design (QbD), (2) mechanistic studies on the palladium-catalyzed synthesis of diarylmethanes, (3) the optimization of microwave-assisted click reactions and Suzuki couplings for use in an undergraduate organic chemistry laboratory manual, and (4) monitoring the progress of organic transformations using Raman spectroscopy.

Synthesis, Characterization, And Photocatalytic Testing Of Titania-Based Aerogels For The Degradation Of Volatile Organic Compounds, Dayton Thomas Horvath

Honors Scholar Theses

The need to degrade volatile organic compounds (VOC’s) has grown with recent economic and environmental concerns. Advanced oxidation processes governing breakdown of VOC’s have received significant attention due to environmentally conscious practices and objectives. Photocatalysis is a logical approach for VOC removal in air because of minimal energy requirements and ease of implementation. Titania with high pore volume and surface area are synthesized using a modified sol-gel method in conjunction with carbon dioxide supercritical drying. Vanadium doping increases the visible absorption of titania aerogels. Solvent removal is achieved using a custom-built high pressure chamber designed for carbon dioxide supercritical drying. …

The Synthesis Of A Homologous Series Of Alkyl Lumazines And Their Application To The Dispersion Of Carbon Nanotubes, William P. Kopcha

Master's Theses

In this thesis, the synthesis of a series of alkyl lumazine surfactants (LC_n) is reported. Their application to the dispersion of both CoMoCAT and HiPco single-walled carbon nanotubes (SWNTs) is examined in detail and the thermal stability and chirality selection properties of dispersions made with these surfactants were compared both between themselves and with an alkyl flavin surfactant (FC₁₂). Lumazine alkyl chain length exhibited some control over the quality and the quantity of SWNTs dispersed. LC₁₀ was deemed most appropriate for comparison with FC₁₂ based on considerations of solubility and nanotube individualization. …

Improved Synthesis Of The Longtailed Mealybug Pheromone, Johanna M. Bakonyi

Master's Theses

No abstract provided.

Investigation Of The Effect Of Xanthophyll Composition On Energy Transfer And Quenching In Light-Harvesting Complexes From The Diatom, Phaeodactylum Tricornutum, Jose L. Robinson Duggon

Master's Theses

No abstract provided.

Selective Oxidations Of Alcohols And Indoles Using The Oxammonium Cation, Joseph Qiu

Honors Scholar Theses

A general procedure for the oxidation of primary alcohols to carboxylic acids, via an aldehyde intermediate, has been developed that supplements a general procedure for the oxidation of alcohols to either aldehydes or ketones. The mechanism of the oxidation of alcohols to generate aldehydes and ketones, as well as the oxidation reaction to generate acids, was explored in a series of relative rate studies. These studies have shown selectivity in the oxammonium cation oxidations, which was demonstrated by sequential, selective oxidation of a compound possessing two different primary alcohol functionalities.

The reactions of the oxammonium cation with nitrogen heterocycles, specifically …

Mechanistic Study Of The Small Molecule Inhibitor Dx-52-1, Junru Cui

Master's Theses

Cell migration is a basic biological process that is fundamental to several normal and disease processes such as embryonic development, tissue repair, immune function, angiogenesis and cancer cell invasion and metastasis. Small organic molecules inhibiting cell migration can be used as both research probes and therapeutic agents. DX-52-1, a semisynthetic derivative of the natural product quinocarmycin (also known as quinocarcin), inhibits the migration of Madin-Darby canine kidney epithelial cells with nanomolar concentration. We have identified galectin-3, a multifunctional protein whose best-known function is its sugar binding ability, as a secondary target of DX-52-1 with functions in cell motility. In addition, …

Towards The Synthesis Of Alpha-Aminogalactosylceramides, Shaun C. Christian

Master's Theses

No abstract provided.

Microwave Spectroscopy And Structures Of Several Substituted Acetylenes And Fluorocarbons, Joseph A. Fournier

Honors Scholar Theses

The structures of two substituted acetylene compounds have been characterized from their microwave rotational spectra. In the first study, two structures of 6-methyl-3-heptyne have been determined. This compound can be thought of as an ethyl group separated from an isobutyl group by a C≡C spacer. Both structures have the ethyl and isobutyl groups eclipsed, consistent with the dominant interaction determining the orientation about the acetylene axis being the weak dispersion attraction between the end groups. One structure is with the isobutyl group in a symmetric conformation and the other with the isobutyl group asymmetric. In addition, the microwave spectrum of …

Hierarchical Subject Inter-Relations In Physical Chemistry, Carl W. David

Chemistry Education Materials

Students mystified by the progression of topics in Physical Chemistry may gain insight into their path through the material if acquainted with the diagrams presented and discussed herein.

Constructed Response Answers In A Multiple-Choice Universe, Carl W. David

Chemistry Education Materials

A scheme is introduced which allows computer readable multiple choice forms used in traditional examinations to be employed for constructed response items.

Methyl Septanoside Hydrolysis As A Measure Of Carbohydrate Ring Flexibility: Substrate Synthesis And Kinetics Analysis, Shawn Michael Miller

Honors Scholar Theses

A number of seven-membered ring systems have been found to have promising enzyme inhibiting properties. The common explanation for their efficacy is the apparent improved flexibility that the ring-system has over smaller rings. In an attempt to probe the validity of this hypothesis, unnatural seven-membered ring carbohydrates have been generated and subjected to kinetics analysis using hydrolysis. In particular, methyl α- and β-D-glycero-D-guloseptanoside were subjected to acid-catalyzed hydrolysis and monitored via HNMR experiments. The rate constants of the reactions were determined and compared to the hydrolysis rate constants of comparable pyranose carbohydrates and found to be significantly faster, indicating an …

Guessing Harmonic Oscillator Wavefunctions Using Maple, Carl W. David

Chemistry Education Materials

The guessing of eigenfunctions is not trivial at higher quantum numbers, no matter what the system being considered. Instead of guessing, one can employ a symbolic calculus progam (Maple in this case) to aid in the reasoning process.

The Driven Harmonic Oscillator In Chemistry, Carl W. David

Chemistry Education Materials

The molecular dynamical simulation of the normal vibrational mode of water which involves H-O-H angle deformation, when driven by an external force, can be used to see how a driven harmonic oscillator, classically, is associated with the infra-red spectrum of water (and the absorption for this particular normal mode).

Using The Morse Potential To Understand Reaction Coördinates Using Maple, Carl W. David

Chemistry Education Materials

The interactions employed in the “linear” reaction A(g)+BC(g) -> AB(g) + C(g) in a “one dimensional world” can be used to illustrate the “reaction coördinate”, using Maple, in a manner which allows students to inspect potential energy surfaces, make contour maps of those surfaces, and conceptually construct the “reaction coördinate” by tracing the local minimum path on the surface created.“one dimensional world” can be used to illustrate the “reaction coördinate”, using Maple, in a manner which allows students to inspect potential energy surfaces, make contour maps of those surfaces, and conceptually construct the “reaction coördinate” by tracing the local minimum …

Frobenius Solution For Legendre's Equation, Rodrigue's Formula And Normalization, Carl W. David

Chemistry Education Materials

The Frobenius solution to Legendre/s equation is developed in detail as is Rodrigue's formula, which is employed to normalize Legendre polynomials.

1s_A 1s_B Overlap Integrals, Analytic And Maple Approches, Carl W. David

Chemistry Education Materials

The calculation of overlap between adjacent orbitals (not on the same center) requires a slight facility with calculus which is quite instructive. That calculation is presented here.

Rationale For Studying Physical Chemistry, Carl W. David

Chemistry Education Materials

The various rationales for studying physical chemistry, and specifically the theoretical component thereof are presented in what is hoped in a coherent package.

The Harmonic Oscillator's Frobenius Solution, Carl W. David

Chemistry Education Materials

The Frobenius solution to the differential equations associated with the harmonic oscillator (QM) is carried out in detail.

The Hartree-Fock Method Applied To Helium's Electrons, Carl W. David

Chemistry Education Materials

The difficulties of applying the Hartree-Fock method to many body problems is illustrated by treating Helium's electrons up to the point where tractability vanishes. Second, the problem of applying Hartree-Fock methods to the helium atom's electrons, when they are constrained to remain on a sphere, is revisited. The 6-dimensional total energy operator is reduced to a 2-dimensional one, and the application of that 2-dimensional operator in the Hartree-Fock mode is discussed.

Multiple-Choice Testing In Science And Technology Courses, Carl W. David

Chemistry Education Materials

Wide spread and continuing use of multiple-choice testing in technical subjects is leading to a mindset amongst students which is antithetical with actual use of intellect.

L'Hopital's Rule In Chemistry: Irreversible Morphing Into Reversible Isothermal Expansions, Carl W. David

Chemistry Education Materials

L'Hopital's Rule is discussed in the cvase of an irreversible isothermal expansion.

Mo Visualization Of Pi Orbitals, Carl W. David

Chemistry Education Materials

In the spirit of trying to convert people to understanding atomic orbitals centered elsewhere than the origin, we continue the discussion of visualizing molecular orbitals, so called LCAO-MO, using various plotting tricks in Maple.