Physical Sciences and Mathematics Commons^™

Synthesis Of Alpha-Methylselenocysteine, Its Relevant Analogues, And An Unnatural Glutathione Disulfide Core, Robert J. Wehrle

Dissertations

Selenoproteins, such as glutathione peroxidase, have gained interest for their ability to act as antioxidants, and their potential to act as anti-cancer agents. Synthesizing and studying selenoproteins can be problematic, however, due to their propensity to degrade from over-oxidation. The degradation from over-oxidation can be avoided by the incorporation of the unnatural amino acid, alpha-methylselenocysteine. A synthesis utilizing methyl malonic esters was used to synthesize protected (R)-alpha-methylselenocysteine efficiently (46% over four steps) and in high enantio-purity (88% enantiomeric excess). Using similar procedures, the (S)-enantiomer was also synthesized as well as a beta-analogue.

The use of enzymes …

Combining Observations Of Soils And Streams To Investigate Trends Caused By Reduced Acid Depositon In The Sleepers River Watershed, Jesse Armfield

Graduate College Dissertations and Theses

Acid deposition forms when emission-derived sulfur dioxide and nitrogen oxides interact with precipitation and was particularly severe in the northeastern US. Effects of acid deposition include declining soil quality due to low pH and base cation leaching, which subsequently altered the composition of soil solution, ground water (GW) and eventually stream water. Because of the high buffering capacity of carbonates, watersheds underlain by carbonate rich rocks have received limited attention in acid deposition studies, however, carbonate weathering by strong anthropogenic acids can increase atmospheric CO2 levels.

Emission reductions due to the Clean Air Act and Amendments has led to a …

Evidence Of Late Quaternary Fires From Charcoal And Siliceous Aggregates In Lake Sediments In The Eastern U.S.A., Joanne P. Ballard

Doctoral Dissertations

The late-glacial transition to the Holocene, 15,000–11,600 cal yr BP, is an enigmatic period of dynamic global changes and a major extinction event in North America. Fire is an agent of disturbance that transforms the environment physically and chemically, and affects plant community composition. To improve understanding of the linkages between fire, vegetation, and climate over the late glacial and Holocene in the eastern U.S., I analyzed lake-sediment cores for charcoal and indicators of wood ash, and compared results to existing pollen records. A new microscopic charcoal record from Anderson Pond, Tennessee revealed high fire activity from 23,000–15,000 cal yr …

Investigations Into The Molecular Mechanisms Of Bacterial Pathogen-Host Interactions: Construction Of A Dual Plasmid System For Incorporation Of Unnatural Amino Acids Into Pseudomonas Syringae Pv. Tomato Dc3000, Scotty D. Raber

Department of Chemistry: Dissertations, Theses, and Student Research

A dual plasmid system for the incorporation of unnatural amino acids into plant pathogen, Pseudomonas syringae pv. tomato DC3000, has been designed. This invention is expected to allow (a) mutations of proteins synthesized by the bacterium, P. syringae pv. tomato DC3000, that can capture molecular targets, especially for such modified proteins secreted by the phytopathogen into the host plant cells of A. thaliana and S. lycopersicum, (b) expression of biological probes in the bacterial species to monitor changes in redox, nutritional, and other small molecule states over pre-, post- and in situ disease stages, and (c) secretion of such …

Degradation Of High Voltage Glass Fiber-Reinforced Polymer Matrix Composites By Aggressive Environmental Conditions, Tianyi Lu

Electronic Theses and Dissertations

Polymer matrix composites reinforced with either E glass or ECR glass fibers-reinforced are used in a variety of high voltage electrical applications because of their advantages like lower weight and cost. However, they can be damaged by aggressive in-service conditions such as high temperature, ultraviolet radiation, moisture, ozone and corrosive environments. Different degradation mechanisms can develop in high voltage PMCs under those extreme environments, which, in turn, can affect the long term structural durability of the composites. A set of PMCs reinforced with ECR-glass and E-glass fibers embedded in four different resins has been investigated in this study. In addition, …

Synthesis And Characterization Of Ph Responsive D-Glucosamine Based Molecular Gelators, Navneet Goyal, Hari P.R. Mangunuru, Bargav Parikh, Sonu Shrestha, Guijun Wang

Chemistry & Biochemistry Faculty Publications

Small molecular gelators are a class of compounds with potential applications for soft biomaterials. Low molecular weight hydrogelators are especially useful for exploring biomedical applications. Previously, we found that 4,6-O-benzylidene acetal protected D-glucose and D-glucosamine are well-suited as building blocks for the construction of low molecular weight gelators. To better understand the scope of D-glucosamine derivatives as gelators, we synthesized and screened a novel class of N-acetylglucosamine derivatives with a p-methoxybenzylidene acetal protective group. This modification did not exert a negative influence on the gelation. On the contrary, it actually enhanced the gelation tendency for many derivatives. The …

An Acid Catalyzed Reversible Ring-Opening/Ring-Closure Reaction Involving A Cyano-Rhodamine Spirolactam, H. Li, H. Guan, X. Duan, J. Hu, Guiren Wang, Qian Wang

Faculty Publications

Cyanamide was introduced into the rhodamine spirolactam framework to produce a colorless and non-fluorescent compound RBCN. It shows a reversible ring-opening/ring-closure process in response to the solution pH, which exhibits an “ON/OFF” switching in its fluorescence. Different from other rhodamine-type dyes, the ring-open form of RBCN is stable in protic solvents under neutral, near neutral and basic conditions, showing a pink color and very strong fluorescence. We also demonstrated the potential of RBCN in live cell imaging.

Botppi, A New Wittig Salt Used In The Synthesis Of 12-(S)-Hydroxy-Eicosatetraenoic Acid [12-(S)-Hete], Michael A. Christiansen, Merritt B. Andrus

Chemistry and Biochemistry Faculty Publications

An efficient route to (Z)-(8-benzyloxy-8-oxooct-3-en-1-yl)triphenylphosphonium iodide, or BOTPPI, is disclosed, complete with full experimental details, NMR spectra, and HRMS data. BOTPPI serves as a surrogate for (Z)-(8-methoxy-8-oxooct-3-en-1-yl)triphenylphosphonium iodide, or MOTPPI, a Wittig salt previously used in two 12-HETE syntheses. BOTPPI has the advantage over MOTPPI of being derived from a sequence for which every intermediate is UV-active and amenable to large-scale chromatographic purification. A formal asymmetric total synthesis of 12-(S)-HETE is also reported, involving a stereoselective phase-transfer catalyzed (PTC) alkylation in its key step.

Speciation, Luminescence, And Alkaline Fluorescence Quenching Of 4-(2-Methylbutyl)Aminodipicolinic Acid (H2mebadpa), Gilles Muller, A. J. Ingram, A. G. Dunpal, R. Dipietro

Gilles Muller

4-(2-Methylbutyl)aminodipicolinic acid (H2MEBADPA) has been synthesized and fully characterized in terms of aqueous phase protonation constants (pKa's) and photophysical measurements. The pKa's were determined by spectrophotometric titrations, utilizing a fully sealed titration system. Photophysical measurements consisted of room temperature fluorescence and frozen solution phosphorescence as well as quantum yield determinations at various pH, which showed that only fully deprotonated MEBADPA2– is appreciably emissive. The fluorescence of MEBADPA2– has been determined to be quenched by hydroxide and methoxide anions, most likely through base-catalyzed excited-state tautomerism or proton transfer. This quenching phenomenon has been quantitatively explored through steady-state and time-resolved fluorescence measurements. …

Speciation, Luminescence, And Alkaline Fluorescence Quenching Of 4-(2-Methylbutyl)Aminodipicolinic Acid (H2mebadpa), Gilles Muller, A. J. Ingram, A. G. Dunpal, R. Dipietro

Faculty Publications, Chemistry

4-(2-Methylbutyl)aminodipicolinic acid (H2MEBADPA) has been synthesized and fully characterized in terms of aqueous phase protonation constants (pKa's) and photophysical measurements. The pKa's were determined by spectrophotometric titrations, utilizing a fully sealed titration system. Photophysical measurements consisted of room temperature fluorescence and frozen solution phosphorescence as well as quantum yield determinations at various pH, which showed that only fully deprotonated MEBADPA2– is appreciably emissive. The fluorescence of MEBADPA2– has been determined to be quenched by hydroxide and methoxide anions, most likely through base-catalyzed excited-state tautomerism or proton transfer. This quenching phenomenon has been quantitatively explored through steady-state and time-resolved fluorescence measurements. …

I. Studies Toward The Synthesis Of Echinodithianic Acid And Ii. The Temperature Dependent Nmr Spectrum Of Methyl N-Acetylsarcosinate, Alan Leroy Love

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

Approaches to the preparation of echinodithianic acid (5) from 2,5-dicarbomethoxy-1,4-dithiane (1) were not successful, due to the inability to carboxylate or carboalkoxylate 1 at carbons 2 and 5. Studies toward the synthesis of 5 utilizing methyl 2-acetamidoacrylate (8) have been investigated. The electrophilic addition of sulfur dichloride to 8 yielded bis-(2-acetamido-2-carbo-methoxyvin-1-yl) sulfide, while the addition of thiocyanogen chloride to 8 produced methyl 2-acetamido-3-thiocyanato-acrylate.

As electrophilic additions of unsymmetrical dipolar reagents to methyl 2-acetamidoacrylate (8) are not reported in the literature, the addition of hydrogen bromide to 8 was studied to determine the orientation effect of the acetamido group.

Methyl 2-acetamido-2-bromopropionate …

Nature Of Non-Biological Decomposition Of Nitrite In Acid Media, Mukkatira Kariappa Mahendrappa

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

Curiosity is the cause of investigations, and the thirst for knowledge originates from it. Many times at the end of investigations, the number of questions raised are greater than those for which answers are sought. Therefore, all the information gathered through scientific investigations may not be of value for immediate application in practical life. Nevertheless, no research can be considered less important than the other because the integration of several scientific findings considered less less important at the time of investigation may reveal something of very high significance. Similarly, the study of various transformation reactions that the added fertilizers undergo …