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Application Of The Picoloyl Group In Carbohydrate Chemistry, Michael Mannino 2019 University of Missouri-St. Louis

Application Of The Picoloyl Group In Carbohydrate Chemistry, Michael Mannino

Dissertations

Stereocontrol of glycosylation reactions is a constant struggle in the field of synthetic carbohydrate chemistry. The application of the picoloyl (Pico) substituent can offer numerous stereocontrolling avenues. The most popular application is the Hydrogen-bond-mediated Aglycone Delivery (HAD) method that provides excellent selectivity in the glycosylation of a variety of sugar substrates. The HAD method relies on the formation of an intermolecular hydrogen bond between the nitrogen atom of the Pico substituent on the glycosyl donor with the hydroxyl group of the glycosyl acceptor. This interaction provides a facial preference for the nucleophilic attack and hence provides powerful stereocontrol for the …


Analysis Of Dl-Amino Acid Ratios In Eggshells Using Reverse Phase-High Pressure Liquid Chromatography, Gergana Milkova 2019 Andrews University

Analysis Of Dl-Amino Acid Ratios In Eggshells Using Reverse Phase-High Pressure Liquid Chromatography, Gergana Milkova

Honors Theses

HPLC methodology was developed to determine the concentrations and ratios of D to L amino acids in emu and ostrich eggshells treated with heat at different temperatures . We aimed to determine an internal standard and how ratios were affected under different conditions. An HPLC method was determined that gave consistent retention times and satisfactory enantioseparation . Calibration curves for each amino acid were developed from single and multi-amino acid containing dilution series producing a model that most closely replicates the eggshell-extracted amino acids.


Enantioselective Copper Catalyzed Alkyne-Azide Cycloaddition By Dynamic Kinetic Resolution, En Chih Liu, Joseph J. Topczewski 2019 Missouri University of Science and Technology

Enantioselective Copper Catalyzed Alkyne-Azide Cycloaddition By Dynamic Kinetic Resolution, En Chih Liu, Joseph J. Topczewski

Chemistry Faculty Research & Creative Works

The copper(I) catalyzed alkyne-azide cycloaddition (CuAAC), a click reaction, is one of the most powerful catalytic reactions developed during the last two decades. Conducting CuAAC enantioselectively would add a third dimension to this reaction and would enable the direct synthesis of α-chiral triazoles. Doing so is demanding because the two precursors have linear geometries, and the triazole product is a flat heterocycle. Designing a chiral catalyst is further complicated by the complex mechanism of CuAAC. We report an enantioselective CuAAC (E-CuAAC), enabled by dynamic kinetic resolution (DKR). The E-CuAAC is high yielding and affords up to 99:1 er. The E-CuAAC …


Drug Improvement And Design Involving G-Protein Coupled Receptors, Gabriel Saliba 2019 Taylor University

Drug Improvement And Design Involving G-Protein Coupled Receptors, Gabriel Saliba

Chemistry & Biochemistry Student Projects

No abstract provided.


A Chemical Overview Of Opioid Receptors And Their Agonists, Noah Kuszak 2019 Taylor University

A Chemical Overview Of Opioid Receptors And Their Agonists, Noah Kuszak

Chemistry & Biochemistry Student Projects

This work is a brief overview of the three main opioid receptors and some current research of the ways we can change the agonists and how they affect the opioid receptor pathway.


Dentin Biomodification Potency Of Proanthocyanidins, David J. Ryker 2019 Taylor University

Dentin Biomodification Potency Of Proanthocyanidins, David J. Ryker

Chemistry & Biochemistry Student Projects

No abstract provided.


Synthesis And Metalation Of Internally Alkylated Porphyrinoids, Alissa Nicole Latham 2019 Illinois State University

Synthesis And Metalation Of Internally Alkylated Porphyrinoids, Alissa Nicole Latham

Theses and Dissertations

The mechanism behind alkyl migration in palladium(II) benzocarbaporphyrins was investigated through the synthesis of a 23-methylcarbaporphyrin. It was found that palladium insertion led to methyl group migration to C21 and it is proposed that this occurs through an oxidative addition onto the palladium metal center, followed by a reductive elimination to transfer the methyl to the internal carbon. A similar rearrangement was observed when 23-methylcarbaporphyrin was reacted with [Rh(CO)2Cl]2 and resulted in the formation of a rhodium(III) complex containing a three-membered rhodacycle. The syntheses of rhodium(I) and rhodium(III) derivatives of other carbaporphyrins, including 21- and 22-methylbenzo-carbaporphyrins, were probed and four …


An Improved Synthesis Of Adefovir And Related Analogues, Timothy P. O'Sullivan, et al 2019 Department of Physical Sciences, Cork Institute of Technology, Cork, Ireland

An Improved Synthesis Of Adefovir And Related Analogues, Timothy P. O'Sullivan, Et Al

Physical Sciences Publications

An improved synthesis of the antiviral drug adefovir is presented. Problems associated with current routes to adefovir include capricious yields and a reliance on problematic reagents and solvents, such as magnesium tert-butoxide and DMF, to achieve high conversions to the target. A systematic study within our laboratory led to the identification of an iodide reagent which affords higher yields than previous approaches and allows for reactions to be conducted up to 10 g in scale under milder conditions. The use of a novel tetrabutylammonium salt of adenine facilitates alkylations in solvents other than DMF. Additionally, we have investigated how …


The Effects Of Reactant Concentration And Air Flow Rate In The Consumption Of Dissolved O2 During The Photochemistry Of Aqueous Pyruvic Acid, Alexis J. Eugene, Marcelo I. Guzman 2019 University of Kentucky

The Effects Of Reactant Concentration And Air Flow Rate In The Consumption Of Dissolved O2 During The Photochemistry Of Aqueous Pyruvic Acid, Alexis J. Eugene, Marcelo I. Guzman

Chemistry Faculty Publications

The sunlight photochemistry of the organic chromophore pyruvic acid (PA) in water generates ketyl and acetyl radicals that contribute to the production and processing of atmospheric aerosols. The photochemical mechanism is highly sensitive to dissolved oxygen content, [O2(aq)], among other environmental conditions. Thus, herein we investigate the photolysis (λ ≥ 305 nm) of 10–200 mM PA at pH 1.0 in water covering the relevant range 0 ≤ [O2(aq)] ≤ 1.3 mM. The rapid consumption of dissolved oxygen by the intermediate photolytic radicals is monitored in real time with a dissolved oxygen electrode. …


Synthesis Of A Sulfur Variant For Treatment Of Trypanosomiasis, Carlos Vera-Esquivel 2019 University of Nebraska at Omaha

Synthesis Of A Sulfur Variant For Treatment Of Trypanosomiasis, Carlos Vera-Esquivel

UNO Student Research and Creative Activity Fair

Previous work in our lab has found diphenyl ether benzylamines showed a successful response with a micromolar concentration of our lead compound to treat the deadly Trypanosamiosis rhodesience. Furthermore, mammalian cell lines saw promising resistance towards damages. The goal of this study was to synthesize a diphenyl thio benzylamine variant. This variant was more active toward T. b. rhodesience but showed more toxicity to both rat 10 (IC50 mM) and human cell lines (HFF, HC-04, U-2 OS, and HEK293). The selectivity index (ratio of toxicity to activity in the same concentration units (SI)) …


Facile And Efficient Synthesis Of Thiosemicarbazone Derivatives With Functionalized Pendant Amines., Anna E Davis 2019 University of Louisville

Facile And Efficient Synthesis Of Thiosemicarbazone Derivatives With Functionalized Pendant Amines., Anna E Davis

College of Arts & Sciences Senior Theses

Bis-thiosemicarbazones are an important class of ligands for the synthesis of transition metal complexes with applications in medicine and electrochemistry.1,2 Among the most studied of these complexation ligands is diacetyl-2,3-bis(N4-methyl-3-thiosemicarbazone) (denoted as ATSM, 1, Figure 1).2,3 Derivatives of 1 with various amines in place of the methylamine of ATSM have previously been reported, including diacetyl (N4-methylthiosemicarbazone-N4′-dimethylthio-semicarbazone) (denoted as ATSM/DM, 2).4 In this work, we pursue the development of a library of ATSM derivatives with a variety of functionalized pendant amines with a range of electronic and steric …


Seasonal Origins Of Soil Water Used By Trees, Scott T. Allen, James W. Kirchner, Sabine Braun, Rolf T. W. Siegwolf, Gregory R. Goldsmith 2019 ETH Zurich

Seasonal Origins Of Soil Water Used By Trees, Scott T. Allen, James W. Kirchner, Sabine Braun, Rolf T. W. Siegwolf, Gregory R. Goldsmith

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

Rain recharges soil water storages and either percolates downward into aquifers and streams or is returned to the atmosphere through evapotranspiration. Although it is commonly assumed that summer rainfall recharges plant-available water during the growing season, the seasonal origins of water used by plants have not been systematically explored. We characterize the seasonal origins of waters in soils and trees by comparing their midsummer isotopic signatures (δ2H) to seasonal isotopic cycles in precipitation, using a new seasonal origin index. Across 182 Swiss forest sites, xylem water isotopic signatures show that summer rain was not the predominant water source …


Metal-Assisted Hydrolysis Reactions Involving Lipids: A Review, Dominique E. Williams, Kathryn B. Grant 2019 University of Richmond

Metal-Assisted Hydrolysis Reactions Involving Lipids: A Review, Dominique E. Williams, Kathryn B. Grant

Chemistry Faculty Publications

This report covers major advances in the use of metal ions and complexes to hydrolyze ester and phosphate ester lipid bonds. These metal-based Lewis acids have been investigated as catalysts to isolate fatty acids from biological sources, as probes to study phospholipid bilayer properties, as tools to examine signal transduction pathways, and as lead compounds toward the discovery of therapeutic agents. Metal ions that accelerate phosphate ester hydrolysis under mild conditions of temperature and pH may have the potential to mimic phospholipase activity in biochemical applications.


Metrics And Methods Used To Compare Student Performance Data In Chemistry Education Research Articles, Michael R. Mack, Cory Hensen, Jack Barbera 2019 University of Washington - Seattle Campus

Metrics And Methods Used To Compare Student Performance Data In Chemistry Education Research Articles, Michael R. Mack, Cory Hensen, Jack Barbera

Chemistry Faculty Publications and Presentations

Quasi-experiments are common in studies that estimate the effect of instructional interventions on student performance outcomes. In this type of research, the nature of the experimental design, the choice in assessment, the selection of comparison groups, and the statistical methods used to analyze the comparison data dictate the validity of causal inferences. Therefore, gathering and reporting validity evidence in causal studies is of utmost importance, especially when conclusions have real policy implications for students and faculty, among other stakeholders. This review examines 24 articles that reported quantitative investigations of the effect of instructional interventions on performance-based outcomes conducted within undergraduate …


Ring Expansion Of Alkylidenecarbenes Derived From Lactams, Lactones, And Thiolactones Into Strained Heterocyclic Alkynes: A Theoretical Study, N. N. Thu Le, J. Just, J. M. Pankauski, Paul R. Rablen, D. M. Thamattoor 2019 Swarthmore College

Ring Expansion Of Alkylidenecarbenes Derived From Lactams, Lactones, And Thiolactones Into Strained Heterocyclic Alkynes: A Theoretical Study, N. N. Thu Le, J. Just, J. M. Pankauski, Paul R. Rablen, D. M. Thamattoor

Chemistry & Biochemistry Faculty Works

Strained cycloalkynes are of considerable interest to theoreticians and experimentalists, and possess much synthetic value as well. Herein, a series of cyclic alkylidenecarbenes—formally obtained by replacing the carbonyl oxygen of four-, five-, and six-membered lactams, lactones, and thiolactones with a divalent carbon—were modeled at the CCSD(T)/cc-pVTZ//B3LYP/6-311+G** and CCSD(T)/cc-pVTZ//CCSD/6-311+G** levels of theory. The singlet carbenes were found to be more stable than the triplets. The strained heterocyclic alkynes formed by ring expansion of these singlet carbenes were also modeled. Interestingly, the C≡C bonds in the five-membered heterocycles, obtained from the rearrangement of β-lactam- and β-lactone-derived alkylidenecarbenes, displayed lengths intermediate between formal …


Carbohydrate Polymers As Controlled Release Devices For Pesticides, Soma Chakraborty, Maria Cleofe Neri-Badang 2019 Ateneo de Manila University

Carbohydrate Polymers As Controlled Release Devices For Pesticides, Soma Chakraborty, Maria Cleofe Neri-Badang

Chemistry Faculty Publications

Controlled release technology addresses problems associated with excessive use of toxic agricultural chemicals. This paper reviews the studies on the use of carbohydrate polymers as controlled release matrices for pesticides. Alginates, starch and its derivatives, chitosan, carboxymethylcellulose and ethylcellulose are some of the natural polymers discussed in this review. The advantages and disadvantages of these polymeric systems as well as the factors that affect pesticide release are presented. A discussion on the polymers’ encapsulation efficiency and release profile is also included, which will aid future researchers in identifying the suitable formulation for controlled release of pesticides. Combination of two polymers, …


Bisthioether Stapled Peptides Targeting Polycomb Repressive Complex 2 Gene Repression, Gan Zhang 2019 CUNY Graduate Center

Bisthioether Stapled Peptides Targeting Polycomb Repressive Complex 2 Gene Repression, Gan Zhang

Dissertations, Theses, and Capstone Projects

Interactions between proteins play a key role in nearly all cellular process, and therefore, disruption of such interactions may lead to many different types of cellular dysfunctions. Hence, pathologic protein-protein interactions (PPIs) constitute highly attractive drug targets and hold great potential for developing novel therapeutic agents for the treatment of incurable human diseases. Unfortunately, the identification of PPI inhibitors is an extremely challenging task, since traditionally used small molecule ligands are mostly unable to cover and anchor on the extensive flat surfaces that define those binary protein complexes. In contrast, large biomolecules such as proteins or peptides are ideal fits …


Synthesis And Evaluation Of Novel Iodine-124 Labeled Nucleoside Analogs As Pet Imaging Agents To Predict Response To Gemcitabine Therapy, Kishore Kumar Gangangari 2019 CUNY Graduate Center

Synthesis And Evaluation Of Novel Iodine-124 Labeled Nucleoside Analogs As Pet Imaging Agents To Predict Response To Gemcitabine Therapy, Kishore Kumar Gangangari

Dissertations, Theses, and Capstone Projects

Gemcitabine (gem) is a nucleoside analog that is used to treat pancreatic cancers (PaCa), which have dismal prognosis and low survival rate. Though gem is used as first line of treatment for PaCa, the response rate is quite low (~30%). Currently, there is no a priori way to determine a responder from a non-responder to gem therapy either invasively or non-invasively. Any biomarker that can act as a prognostic indicator of gem response will greatly aid in selecting responsive patients to gem therapy and provide alternative options such as Folfirinox or other treatments to resistant patient population. Amongst various known …


Photo-Induced Remote C-H Functionalization And New Thioglycoside Donor Development For O-Glycosylation, Shaofu Du 2019 Louisiana State University and Agricultural and Mechanical College

Photo-Induced Remote C-H Functionalization And New Thioglycoside Donor Development For O-Glycosylation, Shaofu Du

LSU Doctoral Dissertations

This dissertation focuses on the method development of C-H functionalization using photo-redox catalysis and the synthesis of new thioglycoside donors towards O-glycosylation. Chapter 1 describes the remote Csp3-H functionalization using photo-redox catalysis. The site-selective and high-yielding conversion of unreactive aliphatic C-H bonds has been a challenge for organic chemists for many years. In this work, inert C-H bonds were successfully converted to more useful C-C, C-N, and C-O bonds via hydrogen atom transfer (HAT), radical translocation and polar crossover. This mechanistic manifold was enacted by visible-light irradiation of o-diazoniaphenyl alkyl sulfones in the presence of Ru(bpy) …


Refinement Of Production Grade Biodiesel, Campbell Axt, Robert B. Hughley Jr., Sydney Ninneman, Jillian Turner 2019 GCSU

Refinement Of Production Grade Biodiesel, Campbell Axt, Robert B. Hughley Jr., Sydney Ninneman, Jillian Turner

The Corinthian

The modified Burton method for the thermal hydrogen-cracking of peanut oil has been investigated in McGill Research Group since 2009. The successful and reliable production of biodiesel has been achieved since 2014. A hydrocarbon with a viscosity similar to Production Grade Diesel will work in modern diesel engines. The current product has a viscosity significantly lower than production grade diesel. The starting material has a viscosity significantly higher than Production Grade Diesel. Current research is investigating methodologies to mix starting material and product to achieve target viscosity.


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