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Full-Text Articles in Physical Sciences and Mathematics

Towards Completely Automated Glycan Synthesis, Matteo Panza Nov 2019

Towards Completely Automated Glycan Synthesis, Matteo Panza

Dissertations

Carbohydrates are ubiquitous both in nature as biologically active compounds and in medicine as pharmaceuticals. Although there has been continued interest in the synthesis of carbohydrates, chemical methods require specialized knowledge and hence remain cumbersome. The need for development of rapid, efficient and operationally simple procedures has come to the fore. This dissertation focuses on the development of a fully automated platform that will enable both experts and non-specialists to perform the synthesis of glycans. Existing automated methods for the synthesis of oligosaccharides are highly sophisticated, operationally complex, and require significant user know-how. By contrast, high performance liquid chromatography (HPLC) …


Chemical Synthesis Of Oligosaccharides From Human Milk, Mithila Dulanjalee Bandara Weerasooriya Mudiyanselage Oct 2019

Chemical Synthesis Of Oligosaccharides From Human Milk, Mithila Dulanjalee Bandara Weerasooriya Mudiyanselage

Dissertations

Human milk oligosaccharides (HMO) are a family of structurally related glycans that are highly abundant in breast milk. Oligosaccharide fraction is the third largest solid component in human milk after lactose and lipids. There is an accumulating evidence that HMO can provide significant benefits to the breast-fed infants. However, understanding of the exact HMO functions is still incomplete due to the lack of individual compounds in sufficient quantities. Therefore, development of expeditious strategies for the chemical synthesis of HMO has been increasingly important. Among all the methods available for oligosaccharide synthesis, armed-disarmed strategy introduced by Fraser-Reid is based on chemoselective …


Aerobic C-C And C-O Bond Formation Reactions Mediated By High-Valent Nickel Species., Sofia Smith, Oriol Planas, Laura Gómez, Nigam Rath, Xavi Ribas, Liviu Mirica, Liviu Mirica Sep 2019

Aerobic C-C And C-O Bond Formation Reactions Mediated By High-Valent Nickel Species., Sofia Smith, Oriol Planas, Laura Gómez, Nigam Rath, Xavi Ribas, Liviu Mirica, Liviu Mirica

Chemistry & Biochemistry Faculty Works

Nickel complexes have been widely employed as catalysts in C–C and C–heteroatom bond formation reactions. While Ni(0), Ni(I), and Ni(II) intermediates are most relevant in these transformations, recently Ni(III) and Ni(IV) species have also been proposed to play a role in catalysis. Reported herein is the synthesis, detailed characterization, and reactivity of a series of Ni(II) and Ni(III) metallacycle complexes stabilized by tetradentate pyridinophane ligands with various N-substituents. Interestingly, while the oxidation of the Ni(II) complexes with various other oxidants led to exclusive C–C bond formation in very good yields, the use of O2 or H2O2 as oxidants led to …


Capabilities And Limitations Of The Spin Hamiltonian Formalism In Single Molecule Magnets, Philip Ferko Jul 2019

Capabilities And Limitations Of The Spin Hamiltonian Formalism In Single Molecule Magnets, Philip Ferko

Dissertations

The rational design of molecular magnetic materials is an ongoing effort involving physics, materials science, and chemistry. A common approach to design of complexes and interpretation of magnetic data is the spin Hamiltonian formalism. In this approach, magnetic data is interpreted through constants extracted from the parameterization of data. In design, certain structural motifs are pursued, rationalized by the minimization or maximization of terms in the spin Hamiltonian. In this work, monometallic complexes were prepared to simplify magnetic behavior and allow the examination of specific factors that influence single molecule magnetism like coordination geometry, ligand identity, symmetry, and spin-orbit coupling. …


The Chemistry And Biology Of Cyclophostin, The Cyclipostins And Related Compounds, Christopher Spilling Jul 2019

The Chemistry And Biology Of Cyclophostin, The Cyclipostins And Related Compounds, Christopher Spilling

Chemistry & Biochemistry Faculty Works

Cyclophostin, the cyclipostins and the salinipostins are structurally related cyclic enolphosphate natural products. This mini review describes their isolation, synthesis and biological activities. In addition, the synthesis and biological activities of monocyclic enolphosphate and mono and bicyclic enolphosphonate analogs are presented.


Building Blocks For Oligosaccharide Synthesis, Mariya Novakova, Mithila Bandara, Catherine Alex Apr 2019

Building Blocks For Oligosaccharide Synthesis, Mariya Novakova, Mithila Bandara, Catherine Alex

Undergraduate Research Symposium

Carbohydrates (sugars or glycans) are involved in many processes and are referred to as the “essential molecules of life.” Our life begins with fertilization, which takes place via carbohydrate-protein recognition. Our journey with sugars continues with human milk that becomes the ideal first food for babies. Oligosaccharides present in human milk (HMOs) can provide prebiotic effects, function as antimicrobial agents, and provide necessary nutrients for the development of the brain and cognition of infants. Throughout our lifetime, sugars are involved in many upkeeping processes and defensive mechanisms including joint lubrication, cell growth, antigenic determination, anti-inflammation, immune response. Presented herein is …


Molecular Assembly Line For Intramolecular Electron Transferring Bimetallic Fe And Mn Cyanometallate Clusters, Austin L. Stelling, Nigam Rath Apr 2019

Molecular Assembly Line For Intramolecular Electron Transferring Bimetallic Fe And Mn Cyanometallate Clusters, Austin L. Stelling, Nigam Rath

Undergraduate Research Symposium

There has been emerging worldwide research dedicated to finding molecular complexes suitable for molecule-based high-density information storage via intramolecular electron transfer. A known cyanoferrate switchable material, Prussian Blue, has inspired research efforts of Holmes et al. to create families of heterometallic Prussian Blue derivatives that display optical and magnetic behavioral transitions with the variation of light and temperature. The task for my undergraduate research project is synthesizing massive switchable molecular clusters containing cyano-bridged Fe and Mn units. During the process, Marcus-Hush theory of electron transfer was an important consideration during the synthesis of tri- and tetranuclear complexes with varying redox …


Comparison Of Hop Derived Humulone Constituents In Beer Using Uv-Vis, Hplc, And Lc-Ms, Aaron I. Boland, Nicholas Viriyasiri, Lorna Espinosa, Hunter Campbell, Kurt Driesner Apr 2019

Comparison Of Hop Derived Humulone Constituents In Beer Using Uv-Vis, Hplc, And Lc-Ms, Aaron I. Boland, Nicholas Viriyasiri, Lorna Espinosa, Hunter Campbell, Kurt Driesner

Undergraduate Research Symposium

Lupulones and humulones are two families of compounds derived from the hop flower (Humulus lupulus), utilized in brewing beer. Isohumulones are produced during the boiling process by isomerization reactions of humulones and are the primary bittering compounds in beer. The concentration in parts per million (ppm) of isohumulone is reported as IBU (International Bittering Units). Measurement of these compounds is valuable to brewers, but is confounded by other constituents in beer which may also absorb at the 275nm wavelength in UV-Vis spectrometry, the industry standard method. 25 samples were measured using UV-Vis, then analyzed by High Precision Liquid Chromatography (HPLC) …


Hplc-Based Automated Synthesis: Building Blocks For The Development Of New Technologies, Hayley B. Steber, Matteo Panza Apr 2019

Hplc-Based Automated Synthesis: Building Blocks For The Development Of New Technologies, Hayley B. Steber, Matteo Panza

Undergraduate Research Symposium

Use of automated technologies is of increasing interest in glycosciences.1 Among the new methodologies, a number of recent advancements have emerged in the area of solid-phase oligosaccharide synthesis.2-3 Demchenko and Stine developed a synthesizer based on a commercial HPLC instrument that was recently improved by the implementation of the autosampler for the delivery of glycosylation promoters.4 Despite the added versatility, the system still lacks complete automation. The foundations of glycan syntheses are acceptors and donors, grouped together under the general term of building blocks. Presented herein is the synthesis of the building blocks of the rhamno and galacto series. We …


Comparison Of Hop Derived Humulone Constituents In Beer Using Uv-Vis, Hplc, And Lc-Ms, Aaron Boland, Nicholas Viriyasiri, Hunter Campbell Apr 2019

Comparison Of Hop Derived Humulone Constituents In Beer Using Uv-Vis, Hplc, And Lc-Ms, Aaron Boland, Nicholas Viriyasiri, Hunter Campbell

Undergraduate Research Symposium

Lupulones and humulones are two families of compounds derived from the hop flower (Humulus lupulus), utilized in brewing beer. Isohumulones are produced during the boiling process by isomerization reactions of humulones and are the primary bittering compounds in beer. The concentration in parts per million (ppm) of isohumulone is reported as IBU (International Bittering Units). Measurement of these compounds is valuable to brewers, but is confounded by other constituents in beer which may also absorb at the 275nm wavelength in UV-Vis spectrometry, the industry standard method. 25 samples were measured using UV-Vis, then analyzed by High Precision Liquid Chromatography (HPLC) …


High Resolution Near-Infrared/Visible Intracavity Laser Spectroscopy Of Small Molecules, Jack Harms Apr 2019

High Resolution Near-Infrared/Visible Intracavity Laser Spectroscopy Of Small Molecules, Jack Harms

Dissertations

Intracavity laser spectroscopy has been used to study the electronic structure of several small molecules. The molecules studied as part of this dissertation include germanium hydride (GeH), copper oxide (CuO), nickel chloride (NiCl), platinum fluoride (PtF), platinum chloride (PtCl), and copper hydroxide (CuOH). This work encompasses five peer-reviewed publications and two submitted manuscripts.


Application Of The Picoloyl Group In Carbohydrate Chemistry, Michael Mannino Apr 2019

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 …


Biosensor Applications Of Electrodeposited Nanostructures, Keith Stine Feb 2019

Biosensor Applications Of Electrodeposited Nanostructures, Keith Stine

Chemistry & Biochemistry Faculty Works

The development of biosensors for a range of analytes from small molecules to proteins to oligonucleotides is an intensely active field. Detection methods based on electrochemistry or on localized surface plasmon responses have advanced through using nanostructured electrodes prepared by electrodeposition, which is capable of preparing a wide range of different structures. Supported nanoparticles can be prepared by electrodeposition through applying fixed potentials, cycling potentials, and fixed current methods. Nanoparticle sizes, shapes, and surface densities can be controlled, and regular structures can be prepared by electrodeposition through templates. The incorporation of multiple nanomaterials into composite films can take advantage of …


Synthetic Ionophores As Non-Resistant Antibiotic Adjuvants, George Gokel, Mohit Patel, Evan Garrad, Joseph Meisel, Saeedeh Negin, Michael Gokel Jan 2019

Synthetic Ionophores As Non-Resistant Antibiotic Adjuvants, George Gokel, Mohit Patel, Evan Garrad, Joseph Meisel, Saeedeh Negin, Michael Gokel

Chemistry & Biochemistry Faculty Works

Antimicrobial resistance is a world-wide health care crisis. New antimicrobials must both exhibit potency and thwart the ability of bacteria to develop resistance to them. We report the use of synthetic ionophores as a new approach to developing non-resistant antimicrobials and adjuvants. Most studies involving amphiphilic antimicrobials have focused on either developing synthetic amphiphiles that show ion transport, or developing non-cytotoxic analogs of such peptidic amphiphiles as colistin. We have rationally designed, prepared, and evaluated crown ether-based synthetic ionophores (‘hydraphiles’) that show selective ion transport through bilayer membranes and are toxic to bacteria. We report here that hydraphiles exhibit a …