Physical Sciences and Mathematics Commons^™

Para-Methoxybenzylidene Acetal-Protected D-Glucosamine Derivatives As Ph-Responsive Gelators And Their Applications For Drug Delivery, Jonathan Bietsch, Logan Baker, Anna Duffney, Alice Mao, Mary Foutz, Cheandri Ackermann, Guijun Wang

Chemistry & Biochemistry Faculty Publications

Carbohydrate-based low molecular weight gelators (LMWGs) are compounds with the capability to self-assemble into complex molecular networks within a solvent, leading to solvent immobilization. This process of gel formation depends on noncovalent interactions, including Van der Waals, hydrogen bonding, and π–π stacking. Due to their potential applications in environmental remediation, drug delivery, and tissue engineering, these molecules have emerged as an important area of research. In particular, various 4,6-O-benzylidene acetal-protected D-glucosamine derivatives have shown promising gelation abilities. In this study, a series of C-2-carbamate derivatives containing a para-methoxy benzylidene acetal functional group were synthesized and characterized. These compounds exhibited good …

Charge-Transfer Interactions Induce Surface Dependent Conformational Changes In Apolipoprotein Biocorona, Achyut J. Raghavendra, Nasser Alsaleh, Jared M. Brown, Ramakrishna Podila

Publications

Upon introduction into a biological system, engineered nanomaterials (ENMs) rapidly associate with a variety of biomolecules such as proteins and lipids to form a biocorona. The presence of “biocorona” influences nano–bio interactions considerably, and could ultimately result in altered biological responses. Apolipoprotein A-I (ApoA-I), the major constituent of high-density lipoprotein (HDL), is one of the most prevalent proteins found in ENM-biocorona irrespective of ENM nature, size, and shape. Given the importance of ApoA-I in HDL and cholesterol transport, it is necessary to understand the mechanisms of ApoA-I adsorption and the associated structural changes for assessing consequences of ENM exposure. Here, …

Studies On Hydroxyl Radical Formation And Correlated Photoflocculation Process Using Degraded Wood Leachate As A Cdom Source, Luni Sun, Kenneth Mopper

Chemistry & Biochemistry Faculty Publications

In this study, we examined hydroxyl radical (•OH) formation with respect to photoreactivity of colored dissolved organic matter (CDOM), the Fenton reaction, and photoflocculation using leachate from decaying wood. The relationship between •OH photoproduction rate and leachate optical properties (UV-visible absorption and fluorescence excitation-emission matrices (EEMS)) was studied during irradiation using a UV solar simulator. The results showed that the •OH photochemical formation rate is strongly related to humic-like fluorescence as characterized by parallel factor analysis (PARAFAC), and that these fluorescence components are more photolabile than most of the other CDOM components. Fourier transform infrared spectroscopy (FT-IR) indicated the photodegradation …

Graphite Oxide As An Efficient Solid Reagent For Esterification Reactions, Maryam Mirzaaghayan, Rabah Boukherroub, Mahshid Rahimifard

Turkish Journal of Chemistry

Esterification of organic acids with alcohols under mild conditions in high yields using graphite oxide, a readily available and inexpensive material, as an effective reagent is described.

Synthesis Of Novel Sugar Diamino Acids, M Thillakan, A Katsifis, D Skropeta

Danielle Skropeta

Sugar amino acids (SAAs) are found in nature as good construction elements for the preparation of peptide mimetics and oiigosaccharides in drug design and development. The synthesis of SAAs is readily accomplished in few steps and more than 40 SAAs have been synthesised to date.2 Sugar amino acids with an additional amino group, the sugar diamino acid (SDAs) would represent a useful expansion to the library of SAAs available because one of the amino group and carboxylic acid is available for peptide coupling and the another amino/azide group allow to do further derivatisation via peptide or click chemistry such as …

High-Yield Cell-Free Protein Synthesis For Site-Specific Incorporation Of Unnatural Amino Acids At Two Sites, Kiyoshi Ozawa, Karin V. Loscha, Kekini V. Kuppan, Choy Theng Loh, Nicholas E. Dixon, Gottfried Otting

Professor Nick E Dixon

Using aminoacyl-tRNA synthetase/suppressor tRNA pairs derived from Methanocaldococcus jannaschii, an Escherichia coli cell-free protein production system affords proteins with site-specifically incorporated unnatural amino acids (UAAs) in high yields through the use of optimized amber suppressor tRNACUA opt and optimization of reagent concentrations. The efficiency of the cell-free system allows the incorporation of trifluoromethyl-phenylalanine using a polyspecific synthetase evolved previously for p-cyanophenylalanine, and the incorporation of UAAs at two different sites of the same protein without any re-engineering of the E. coli cells used to make the cell-free extract.

Effect Of Organic Solvents On The Separation Of Benzoic Acids By Capillary Electrophoresis, Young J. Lee, William E. Price, Margaret Sheil

William E. Price

The effect of organic modifiers on the separation of a number of closely related isomeric benzoic acids by capillary electrophoresis is described. It is shown that while a single modifier concentration cannot help resolve the entire electropherogram, organic modifiers do significantly enhance the resolution of parts of the separation system by comparison with 40 mmol l-1 phosphate buffer. The effects on separation and retention times are discussed in terms of the effects on electroosmotic flow and the electrophoretic mobilities of the charged solutes. The effects were found to be modifier specific, although the trends were in the same direction (ie., …

Ellagic Acid-Mediated Ck2 Inhibition;A Natural, Multifunctional Strategy To Trigger Cervical Cancer Cell Death In Vitro And In Vivo, Hanan F. Mohammad

ETD Archive

Targeting CK2 for cancer therapy has proven effective in inhibiting tumor growth in several histology's. The main goal of this study was to acquire pre-clinical data on a naturally occurring CK2-inhibitor (ellagic acid) in support of a human clinical trial. In vitro analysis included testing the spectrum of ellagic acid anti-cancer activity, defining the mode of growth inhibition in cancer cells and its impact on biochemical and molecular pathways. In vivo studies included determination of ellagic acid inhibitory effect in animal tumor models and toxicity analysis. We found that CK2 inhibition mediated by ellagic acid, was effective in inhibiting the …

Boronic Acid Macroligands For Glycomics Applications, Poornima Pinnamaneni

ETD Archive

Cell surface carbohydrates existing as glycoproteins and glycolipids represent the first information about the cell with the outside world and are closely involved in various biological processes such as cell communication, and the molecular recognition and cell targeting. However, the mechanisms of most of the processes at the molecular level are still unclear. It is therefore very important to develop specific carbohydrate-binding molecules for a fast, efficient, sensitive and accurate analysis of complex carbohydrates structures and functions, known as glycomics. In addition, certain carbohydrate-binding molecules can be used in medical applications such as biomarkers for diseases diagnosis and targeted drug …

High-Yield Cell-Free Protein Synthesis For Site-Specific Incorporation Of Unnatural Amino Acids At Two Sites, Kiyoshi Ozawa, Karin V. Loscha, Kekini V. Kuppan, Choy Theng Loh, Nicholas E. Dixon, Gottfried Otting

Faculty of Science - Papers (Archive)

Using aminoacyl-tRNA synthetase/suppressor tRNA pairs derived from Methanocaldococcus jannaschii, an Escherichia coli cell-free protein production system affords proteins with site-specifically incorporated unnatural amino acids (UAAs) in high yields through the use of optimized amber suppressor tRNA_CUA opt and optimization of reagent concentrations. The efficiency of the cell-free system allows the incorporation of trifluoromethyl-phenylalanine using a polyspecific synthetase evolved previously for p-cyanophenylalanine, and the incorporation of UAAs at two different sites of the same protein without any re-engineering of the E. coli cells used to make the cell-free extract.

Selective Reduction Of Hydroperoxyeicosatetraenoic Acids To Their Hydroxy Derivatives By Apolipoprotein D: Implications For Lipid Antioxidant Activity And Alzheimer's Disease, Surabhi Bhatia, Bianca Knoch, Jenny Wong, Woojin Scott Kim, Paul Else, Aaron J. Oakley, Brett Garner

Faculty of Science - Papers (Archive)

ApoD (apolipoprotein D) is up-regulated in AD (Alzheimer's disease) and upon oxidative stress. ApoD inhibits brain lipid peroxidation in vivo, but the mechanism is unknown. Specific methionine residues may inhibit lipid peroxidation by reducing radical-propagating L-OOHs (lipid hydroperoxides) to non-reactive hydroxides via a reaction that generates MetSO (methionine sulfoxide). Since apoD has three conserved methionine residues (Met49, Met93 and Met157), we generated recombinant proteins with either one or all methionine residues replaced by alanine and assessed their capacity to reduce HpETEs (hydroperoxyeicosatetraenoic acids) to their HETE (hydroxyeicosatetraenoic acid) derivatives. ApoD, apoDM49-A and apoDM157-A all catalysed the reduction of HpETEs to …

Importance Of Secondary Sources In The Atmospheric Budgets Of Formic And Acetic Acids, Fabien Paulot, Debra Wunch, John D. Crounse, G C. Toon, Dylan B. Millet, Peter F. Decarlo, C Vigouroux, Nicholas M. Deutscher, G Gonzalez Abad, Justus Notholt, Thorsten Warneke, J Hannigan, Carsten Warneke, Joost A. De Gouw, Edward Dunlea, M De Maziere, David W. Griffith, P Bernath, J L. Jimenez, Paul O. Wennberg

Faculty of Science - Papers (Archive)

We present a detailed budget of formic and acetic acids, two of the most abundant trace gases in the atmosphere. Our bottom-up estimate of the global source of formic and acetic acids are ~1200 and ~1400 Gmol yr−1, dominated by photochemical oxidation of biogenic volatile organic compounds, in particular isoprene. Their sinks are dominated by wet and dry deposition. We use the GEOS-Chem chemical transport model to evaluate this budget against an extensive suite of measurements from ground, ship and satellite-based Fourier transform spectrometers, as well as from several aircraft campaigns over North America. The model captures the seasonality of …

Synthesis Of Novel Sugar Diamino Acids, M Thillakan, A Katsifis, D Skropeta

Faculty of Science - Papers (Archive)

Sugar amino acids (SAAs) are found in nature as good construction elements for the preparation of peptide mimetics and oiigosaccharides in drug design and development. The synthesis of SAAs is readily accomplished in few steps and more than 40 SAAs have been synthesised to date.2 Sugar amino acids with an additional amino group, the sugar diamino acid (SDAs) would represent a useful expansion to the library of SAAs available because one of the amino group and carboxylic acid is available for peptide coupling and the another amino/azide group allow to do further derivatisation via peptide or click chemistry such as …

Influence Of Polyunsaturated Fatty Acids On Intestinal Barrier Function During Colitis, Bianca Knoch, Warren C. Mcnabb, Nicole Roy

Faculty of Science - Papers (Archive)

Tight junction proteins are important for intestinal homeostasis. They prevent paracellular transport of large molecules and maintain cell polarity. Impaired tight junction function leads to a more permeable intestinal epithelial barrier and therefore potentially increases disease risk. Limited information is available concerning the effects of food components on the intestinal barrier, particularly paracellular permeability and tight junction proteins. In vitro studies with intestinal epithelial cells and in vivo studies using animal models have demonstrated that dietary n-3 and n-6 polyunsaturated fatty acids (PUFAs), particularly n-3, can reduce intestinal inflammation and permeability. PUFAs can induce transcriptional regulators which may act in …

Importance Of Secondary Sources In The Atmospheric Budgets Of Formic And Acetic Acids, Fabien Paulot, Debra Wunch, John D. Crounse, G C Toon, Dylan B. Millet, Peter F. Decarlo, C Vigouroux, Nicholas M. Deutscher, G Gonzalez Abad, J Notholt, Thorsten Warneke, J Hannigan, Carsten Warneke, Joost A. De Gouw, Edward Dunlea, M. De Maziere, David W. Griffith, P Bernath, J L. Jimenez, Paul O. Wennberg

Faculty of Science - Papers (Archive)

We present a detailed budget of formic and acetic acids, two of the most abundant trace gases in the atmosphere. Our bottom-up estimate of the global source of formic and acetic acids are ∼1200 and ∼1400 Gmol/yr, dominated by photochemical oxidation of biogenic volatile organic compounds, in particular isoprene. Their sinks are dominated by wet and dry deposition. We use the GEOS-Chem chemical transport model to evaluate this budget against an extensive suite of measurements from ground, ship and satellite-based Fourier transform spectrometers, as well as from several aircraft campaigns over North America. The model captures the seasonality of formic …

Antimycobacterial Activity Of Cinnamate-Based Esters Of The Triterpenes Betulinic, Oleanolic And Ursolic Acids, Tanud Tanachatchairatana, John B. Bremner, Ratchanaporn Chokchaisiri, Apichart Suksamrarn

Faculty of Science - Papers (Archive)

Betulinic acid, oleanolic acid and ursolic acid have been modified at the C-3 position to cinnamate-based esters and in vitro antimycobacterial activity against Mycobacterium tuberculosis H₃₇Ra has been determined. The results indicated that modification of the parent structures of betulinic acid, oleanolic acid and ursolic acid to the p-coumarate and, in the case of the latter two triterpenes, the ferulate ester analogues resulted in high antimycobacterial activity. Structure–activity relationships within the lupane, oleanane and ursane analogues and between these triterpenes are discussed.

Reactions Of Atomic Carbon With Acid Chlorides, Daniel B. Herrick

Honors Theses

This thesis is the first report of reactions of atomic carbon with acid chlorides. Carbon is known to react with phosgene to afford dichlorocarbene. We report a similar reaction with carbon and acid chlorides, generating alkylchlorocarbenes. We examine both the nature of the carbene products generated through deoxygenation and the general reactivity of carbon with the acid chlorides. We report two ways in which carbon reacts with acid chlorides. First, as expected from prior work with phosgene, carbon deoxygenates the carbonyl group yielding alkylchlorcarbenes, which rearrange as expected. Second, carbon abstracts the chlorine, and generates the acyl radical, which, in …

Free Fatty Acids From The Crude Hexane Extract Of The Aerial Parts Of Heliotropium Indicum Linn. Growing In Phitsanulok, Thailand, Theeraphan Machan, Jurgen Korth, Boonsom Liawruangrath, Saisunee Liawruangrath, Apiwat Baramee, Stephen G. Pyne

Faculty of Science - Papers (Archive)

Sixteen free fatty acids from the crude hexane extract of the aerial parts of Heliotropium indicum Linn. growing in Phitsanulok, Thailand, have been identified after conversion to their methyl esters with boron trifluoride-methanol followed by quantification by GC-FID and identification by GC-MS analysis. They accounted for 95% of the chromatographable components, with 9,12-octadecadienoic acid, (39.7%), 9-octadecenoic acid (32.4%), hexadecanoic acid (14.2%) and octadecanoic acid (5.1%), as the major constituents. A small amount of 6,10,14-trimethyl-2-pentadecanone and 3,7,11,15-tetramethyl-2-hexadecen-1-ol as well as a homologous series of n-alkanes present at trace level and ranging from C₂₅ to C₃₁ was also found …

Humic And Fulvic Acids: Effects On Plant Nutrition And Growth, Jason Tew

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

Humic substances are reported to improve plant growth and nutrient uptake, with iron the most studied nutrient. The most common forms of iron in soils are iron oxides, which are stable under aerobic conditions and unavailable for plant uptake. Iron deficient plants become chlorotic, which reduces growth and yield. To determine if humic substances can reduce iron chlorosis, five commercially available organic acids were tested on maize grown in sand columns at high pH. The dry granular humic acid from Aldrich Chemical Company applied at 84.4 g/liter of sand by volume (5% by mass) and 1 g/liter added with irrigation …

Characterization Of Microbial Processes That Degrade Chlorinated Solvents In A Constructed Wetland Using Organic Acid And Inorganic Anion Concentration Profiles, Chad B. Bondurant

Theses and Dissertations

Chlorinated solvents have been used in industrial cleaning and degreasing processes in the United States since the early 1900s, and their induction into the environment increased significantly with the growth of industrial processes over the past century. PCE, TCE and their daughter products have been associated with a number of human health concerns and are currently the most common contaminants found in groundwater in the United States. Wetlands possess characteristics necessary for the complete degradation of chlorinated ethenes by microorganisms via anaerobic and aerobic regions that foster the necessary oxidation-reduction conditions. Organic acid and inorganic anion concentrations were evaluated in …

Effect Of Organic Solvents On The Separation Of Benzoic Acids By Capillary Electrophoresis, Young J. Lee, William E. Price, Margaret Sheil

Faculty of Science - Papers (Archive)

The effect of organic modifiers on the separation of a number of closely related isomeric benzoic acids by capillary electrophoresis is described. It is shown that while a single modifier concentration cannot help resolve the entire electropherogram, organic modifiers do significantly enhance the resolution of parts of the separation system by comparison with 40 mmol l-1 phosphate buffer. The effects on separation and retention times are discussed in terms of the effects on electroosmotic flow and the electrophoretic mobilities of the charged solutes. The effects were found to be modifier specific, although the trends were in the same direction (ie., …

Low‐Cost Technique For Preparing N‐Sb2S3/P‐Si Heterojunction Solar Cells, O. Savadogo, K. C. Mandal

Faculty Publications

No abstract provided.

Enantioselective Synthesis Of (-)-Retigeranic Acid, Teresa L. Bryant

Theses & Honors Papers

A new enantioselective convergant approach to Retigeranic acid (1) using (2+3} cyclopentene annulation methodology was used. A vinyl cyclopropane (8) intermediate was formed from the enone (9) and the bromoester (10). This product (8) was then pyrolized to yield the triquinane ring system (7). The pyrolysis product was reduced and saponified to give one enatiomer of Retigeranic acid (1) in good yield.

Reduction Of N-Protected Amino Acids To Amino Alcohols And Subsequent Re-Oxidation To Original N-Protected Amino Acids, Val S. Goodfellow

Undergraduate Honors Capstone Projects

For the synthesis of certain molecules of interest in Dr. Richard Olsen's laboratory it was necessary to produce N-protected a-amino alcohols from N-protected amino acids and subsequently, after further synthesis steps, to oxidize the hydroxyl functionalities of these molecules back to carboxylic acids. A number of methods are known for the reduction of carboxylic acids to alcohols; several methods are also reported in the chemical literature for the oxidation of alcohols to carboxylic acids. The problem in finding a suitable general method, is that the amino acid side chains affect the re activity and chemistry differently in each specific case. …

High Pressure Liquid Chromatographic Methods For The Separations Of Derivatized Alpha-Keto Acids And Thiamine Phosphate Esters, Bruce Clark Hemming

Theses and Dissertations

Improved methods have been developed for separation of a-keto acid derivatives and for thiamine and its phosphate esters. Linear gradient reverse phase chromatography using ion-pair formation provides baseline resolution for a seven-component homologous series of a-keto acid dinitrophenylhydrazones having increasing carbon chain lengths. Branched-chain keto acids can also be separated. Aldehyde derivatives were examined as possible interfering compounds. Peak identification in biological material was confirmed for pyruvate by an enzymic peak shift technique. Monitoring near 365 nm permits low nanogram detection. Preliminary studies of keto acids in biological material illustrate the method's applicability. The same system with slight changes separates …

The Synthesis Of Novel Macrocyclic Multidentate Compounds From Dioxodioic Acids (1), R. Elliott Asay

Theses and Dissertations

A series of novel macrocyclic multidentate crown compounds have been prepared from a series of dioxodioic acids. The dioxodioic acids were prepared by treating various oligoethylene glycols or amines with maleic, succinic, citraconic, and glutaric anhydrides. The crown compounds were then synthesized from the dioxodioic acid chlorides obtained from the diacids and various oligoethylene glycols or ethylene diamine.

A Potentiometric Method, A Convenient And Rapid Technique For Determination Of The Thermodynamics Of Ionization Reactions For Water, Weak Acids, And Some Slightly Soluble Salts In Aqueous Organic Mixed Solvents, Charanai Panichajakul

Theses and Dissertations

A potentiometric method which is devised to be rapid and convenient for determining ionization constants for water, weak acids (or bases), and certain solids in mixed solvents is described. The method has been applied to the determination of ionization for water, acetic acid, benzoic acid, and phenol and the solubility product constant for silver chloride in mixtures of water with methanol, ethanol, acetone, tetrahydrofuran, and p-dioxane containing from 0 to 70 mass percent organic co-solvent at several temperatures between 10 and 40°C. Results are used to study the thermodynamics of ionization in each mixture which is discussed relative to various …

A Kinetic Analysis Of The Iodination Of Pyruvic Acid And Pyruvate Esters, Mohamed M. Fahmi Hegazi

All Master's Theses

In the present work the relative rates of iodination of pyruvic acid and ethyl and methyl pyruvate have been compared at 25.0° C. These studies allow the determination of the respective free energies of activation for these processes. Measurements have also been carried out at various temperatures to determine the enthalpies and entropies of activation for the spontaneous and base catalysed iodinations of these pyruvate systems. The present thesis also includes a comparison of the solvent deuterium isotope effects associated with the spontaneous rate of iodination of pyruvic acid and the alkyl pyruvates. Also, the catalytic rate coefficients associated with …

The Synthesis And Reactions Of 8-Carboxy Isatoic Anhydride, James E. Scheirer

Chemistry Honors Papers

This 34 page thesis examines the preparation and characterization of 8-carboxy isatoic anhydride and the study of its reactions, leading to the synthesis of compounds of new composition.

The Content Of Essential Amino Acids In 1950 Alfalfa Hay Grown In Utah Soil Treated With Different Fertilizers, Adriana Lanting Kunkel

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

Application of fertilizers to soils to increase production yields has raised questions concerning the effect of fertilizer on chemical composition of plants. With the development of accurate, sensitive microbiological methods for the determination of amino acid in protein, speculations concerning amino acid content have been supplanted by acquisition of facts.

The effect of the different fertilizer applications on alfalfa yield has been discussed by Jones, et al (5). Also, some work has been done to determine the effect different fertilizers might have on the amino acid content of plant material. Some values (1,3,12) have been reported for the amino acid …