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Nmr Spectroscopic Properties Of Nucleotides, And A New Method Of Numeric Calculation Of Raman Intensities For Organic Molecules, William R. Ehrhardt 2018 Missouri State University

Nmr Spectroscopic Properties Of Nucleotides, And A New Method Of Numeric Calculation Of Raman Intensities For Organic Molecules, William R. Ehrhardt

MSU Graduate Theses

General and accurate computational methodologies are currently lacking for large chemical systems. This is primarily due to the computational expense required to perform calculations on systems with one hundred or more atoms. Calculated spectroscopic properties could aid in the process of elucidating structural features of large biologically relevant molecules if accurate and inexpensive methods are developed. Towards this end the first steps were taken to design a general methodology for predicting NMR chemical shifts of large nucleic acid systems. It was found that HF and semi-empirical methods were not sufficient for optimization of nucleobases, and therefore larger nucleotide or nucleic ...


Synthesis, Characterization, And Applications Of Ammonium/Phosphonium Chitosan Derivatives For Investigative Dna Interactions, Quinton Kirk Wyatt 2018 Missouri State University

Synthesis, Characterization, And Applications Of Ammonium/Phosphonium Chitosan Derivatives For Investigative Dna Interactions, Quinton Kirk Wyatt

MSU Graduate Theses

Chitosan is examined as a non-viral vector capable of efficient gene delivery due to its favorable properties such as biodegradability, biocompatibility, and is non-toxic to mammalian cells. Cell modifications and vector permeability are enhanced in non-viral vectors that incorporate electrostatic interactions. This work synthesizes cationic (N+, P+) chitosan derivatives, to enhance electrostatic interactions towards nucleotides, using amide coupling agents EDC and HOBt. The final chitosan derivatives will bear cationic functional groups (N+, P+) with various alkyl groups (Me, Et, Pr, Ph) to examine their affinities to nucleotides and antifungal properties. mPEG grafted cationic chitosan derivatives were also synthesized to examine ...


Safe Use Of Hydrogen Peroxide In The Organic Lab, Patrick Dussault 2018 University of Nebraska-Lincoln

Safe Use Of Hydrogen Peroxide In The Organic Lab, Patrick Dussault

Organic Peroxides: Safety Issues

The article describes good practices for use of hydrogen peroxide (H2O2) in an organic lab setting. Major headings include:

Leading references; Toxicity; Physical properties; Chemical properties; Stability and incompatibilities; Confinement/pressure; and, References to accidents involving H2O2.


Alkene Ozonolysis In The Academic Lab, Patrick Dussault 2018 University of Nebraska-Lincoln

Alkene Ozonolysis In The Academic Lab, Patrick Dussault

Organic Peroxides: Safety Issues

The following information is offered as a guide based upon our experience with application of ozone for organic oxidations and hydroperoxide synthesis. Please send suggestions, requests, or corrections to pdussault1@unl.edu.

Introduction and leading references

Overview of ozonolysis: Mechanism, Substrate reactivity, Typical reaction conditions, Reaction monitoring, Reaction work-ups

Safety Issues

Acknowledgements:

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The following provides a brief introduction to the application of ozonolysis within academic labs. Ozonolysis remains among the most frequently used of methods for oxidative cleavage of alkenes. While best known as a means by which to introduce aldehydes and ketones, ozonolysis can also be used to generate ...


Working With Organic Peroxides In The Academic Lab, Patrick Dussault 2018 University of Nebraska-Lincoln

Working With Organic Peroxides In The Academic Lab, Patrick Dussault

Organic Peroxides: Safety Issues

ABSTRACT: The following is a brief introduction to peroxide safety from the viewpoint of a synthetic chemist. Major topics include: classes of organic peroxides; peroxide reactivity; hazard identification and minimization; reaction monitoring; and, hazards associated with auto-oxidation of peroxidizable solvents.

KEYWORDS: peroxide, hydroperoxide, hydroperoxyacetal, ozonide, perester, dihydroperoxide, monoperoxyacetal, active oxygen, peroxide strips, TLC indicator, self-accelerating decomposition, radical, exothermicity, transition metals.

CONTENTS: 1. Literature resources 2. Major classes of peroxides 3. Basis for peroxide reactivity 4. Determining reactivity and minimizing hazards a. Steps to take before an experiment b. Minimizing hazard during reactions c. Monitoring reactions d. Working with isolated peroxides ...


Synthesis Of 2-Thiouracil And 2-Thiothymine Peptide Nucleic Acid Monomers Compatible With Fmoc-Based Oligomerization, Timothy Martin-Chan 2018 The University of Western Ontario

Synthesis Of 2-Thiouracil And 2-Thiothymine Peptide Nucleic Acid Monomers Compatible With Fmoc-Based Oligomerization, Timothy Martin-Chan

Electronic Thesis and Dissertation Repository

Pseudo-complementary nucleobases are modified nucleobases which exhibit normal base pairing with unmodified complementary nucleobases; however, will not undergo stable base pairing with other pseudo-complementary nucleobases. The pseudo-complementary nature of these bases is of interest for the synthesis of pseudo-complementary peptide nucleic acid (pcPNA) oligomers, which are capable of binding targets in double-stranded DNA through a double duplex strand invasion. Until recently, pcPNAs were synthesized via Boc-based oligomerization chemistry which is currently less popular than the Fmoc-based strategy.

This research describes the development of a Fmoc protected thiouracil PNA monomer with an acid labile protecting group for use in standard SPPS ...


Open Resonance Assisted Hydrogen Bonds And Competing Quasiaromaticity, Yen H. Nguyen, Bryan J. Lampkin, Amrit Venkatesh, Arkady Ellern, Aaron J. Rossini, Brett VanVeller 2018 Iowa State University

Open Resonance Assisted Hydrogen Bonds And Competing Quasiaromaticity, Yen H. Nguyen, Bryan J. Lampkin, Amrit Venkatesh, Arkady Ellern, Aaron J. Rossini, Brett Vanveller

Chemistry Publications

The delocalization of electron density upon tautomerization of a proton across a conjugated bridge can alter the strength of hydrogen bonds. This effect has been dubbed resonance-assisted hydrogen bonding (RAHB) and plays a major role in the energetics of the tautomeric equilibrium. The goal of this work was to investigate the role that π-delocalization plays in the stability of RAHBs by engaging other isomerization processes. Similarly, acid-base chemistry has received little experimental attention in studies of RAHB and we address the role that acid-base effects play in the tautomeric equilibrium. We find that π-delocalization and the disruption of adjacent aromatic ...


Investigation Of Vaporization Enthalpies And Vapor Pressures Of Organic Compounds By Correlation Gas Chromatography, Carissa Nelson 2018 University of Missouri, St. Louis

Investigation Of Vaporization Enthalpies And Vapor Pressures Of Organic Compounds By Correlation Gas Chromatography, Carissa Nelson

Dissertations

Thermodynamic properties of organic compounds are useful to scientists and manufacturers in many areas of research and technology. This work focuses on measuring and reporting these properties on materials of commercial, environmental and scientific interest. Vaporization enthalpies and vapor pressures of several organic compounds have been studied using correlation gas chromatography (CGC) and are reported here as well as in recent publications. The CGC method allows for the indirect measurement of these properties in instances where these materials are available only in mixtures or in very small amounts.

The qualities of these measurements for any chosen target are directly related ...


Catalytic Functionalization Of Organoaluminum Reagents And Olefins By Cross-Coupling With Copper And Nickel, Bijay Shrestha 2018 University of New Mexico

Catalytic Functionalization Of Organoaluminum Reagents And Olefins By Cross-Coupling With Copper And Nickel, Bijay Shrestha

Chemistry ETDs

This thesis is divided into two parts. The first part focuses on the Cu-catalyzed cross-coupling of organoaluminum reagents with organohalides. One of the most powerful tools for the construction of C-C bonds is cross-coupling. But, this reaction is predominantly catalyzed by Pd, a rare and expensive transition metal, which inevitably makes the process unsustainable in the long-term. Furthermore, Pd-catalyzed cross-coupling also shows low tolerance for alkyl and heteroaryl substrates because of β-hydride elimination and catalyst deactivation, respectively. Although these issues remain largely solved by using sterically hindered and electron-rich ligands, however making these types of ligands is synthetically challenging and ...


Visible Light Generation Of High-Valent Corrole-Manganese(V)-Oxo Intermediates And Biomimetic Studies Of The Oxidation Of Organic Sulfides Catalyzed By Manganese Corroles With Iodobenzene Diacetate, Davis Ray Ranburger 2018 Western Kentucky University

Visible Light Generation Of High-Valent Corrole-Manganese(V)-Oxo Intermediates And Biomimetic Studies Of The Oxidation Of Organic Sulfides Catalyzed By Manganese Corroles With Iodobenzene Diacetate, Davis Ray Ranburger

Masters Theses & Specialist Projects

High-valent transition metal-oxo intermediates play essential roles as active oxidizing species in enzymatic and biomimetic catalytic systems. Extensive research has been conducted on a variety of transition metal catalysts being studied as models for the ubiquitous cytochrome P450 enzymes. In doing so, the production of enzyme-like oxidation catalysts and probing studies on the sophisticated oxygen atom transfer mechanism are taking place.

In this work, visible-light irradiation of highly-photo-labile corrole-manganese(IV) bromates and chlorates was studied in two corrole systems with differing electronic environments, i.e. 5,10,15-trisphenylcorrole (H3TPC) and 5,10,15- tris(pentafluorophenyl)corrole (H3TPFC). In ...


Photochemical Investigation Of High-Valent Metal-Oxo Intermediates Containing Corrole And Light-Harvesting Porphyrin Ligands, Jonathan Malone 2018 Western Kentucky University

Photochemical Investigation Of High-Valent Metal-Oxo Intermediates Containing Corrole And Light-Harvesting Porphyrin Ligands, Jonathan Malone

Masters Theses & Specialist Projects

In enzymatic and synthetic catalytic oxidations, high-valent iron-oxo intermediates play a vital role as the active oxidant. In this regard, many synthetic metal catalysts are designed as biomimetic models to resemble the active site of Cytochrome P450 enzymes (P450) which are the predominant oxidation catalysts in nature. Vitamin B12 cofactors, with a corrole-like structure corrin, are also utilized in some of the more difficult reactions in nature such as rearrangement and reductase reactions.

In this work, application of the promising photochemical method to corrolecontaining ligands systems showed much success in the generation of manganese(V)-oxo corrole intermediates using two ...


Design, Synthesis And Study Of Redox And Optoelectronic Properties Of Aromatic Oxidants And Polycyclic Aromatic Hydrocarbons, Mohammad Mosharraf Hossain 2018 Marquette University

Design, Synthesis And Study Of Redox And Optoelectronic Properties Of Aromatic Oxidants And Polycyclic Aromatic Hydrocarbons, Mohammad Mosharraf Hossain

Dissertations (2009 -)

Organic materials play a significant role for the next generation photovoltaic devices that convert solar energy into usable forms of energy. In this regard, polycyclic aromatic hydrocarbons (PAHs) are fundamental tools in the developing area of molecular electronics and photovoltaics as they show excellent optical/electronic properties and are well-suited for applications in such developing areas as flexible display devices, field effect transistors and solar cell panels. Design and synthesis of novel materials for photovoltaics applications would require the proper understanding the mechanism of charge transport and identification of the structural features necessary in a particular molecular wire or PAH ...


The Photodynamic And Structural Analyses Of Advanced Materials For Solar Fuel Conversion, Brian Pattengale 2018 Marquette University

The Photodynamic And Structural Analyses Of Advanced Materials For Solar Fuel Conversion, Brian Pattengale

Dissertations (2009 -)

Mitigating the current and future climate and pollution issues that have been brought on by the combustion of fossil fuels is of utmost importance and will rely on, in part, the availability of renewable fuel sources. Of the possible sources of energy, solar is abundant, but must be harnessed efficiently and stored as a solar fuel to overcome the current storage issues that limit photovoltaic cells. One such fuel, H2(g), represents a carbon-neutral source of energy if it can be efficiently liberated from water via the water splitting reaction. Thus, much attention is focused on designing materials to perform ...


Advances In Amino Acid Analysis For Marine Related Matrices And Its Application To Coastal Shelf Settings In The Canadian Arctic, Rachel M. McMahon 2018 Old Dominion University

Advances In Amino Acid Analysis For Marine Related Matrices And Its Application To Coastal Shelf Settings In The Canadian Arctic, Rachel M. Mcmahon

OEAS Theses and Dissertations

Amino acids comprise up to 50% of organic matter in cellular material and are a major fraction of oceanic organic carbon. Amino acids are also considered highly labile during organic matter recycling, making them useful proxies for organic carbon cycling. Nevertheless, analysis of individual amino acids has been burdened by lengthy derivatization and complex analysis since the 1950s. In this thesis, I describe the modification of advanced analytical techniques, developed in the biomedical field, for analysis of marine matrices which allow the determination of at least 40 amino acids without the need for lengthy sample preparation and derivatization, twice the ...


Rearrangements Of Fluorinated Cyclopropylamines As A Novel Approach Toward Fluoroalkene-Based Peptidomimetics, Igor Mezentsev, Vera Zaborova 2018 Moscow South-Eastern School named after V. I. Chuikov

Rearrangements Of Fluorinated Cyclopropylamines As A Novel Approach Toward Fluoroalkene-Based Peptidomimetics, Igor Mezentsev, Vera Zaborova

The International Student Science Fair 2018

"Organofluorine molecules have been widely applied in various research fields because of the unique properties of fluorine atoms. One type of fluorinated compounds is fluoroalkene-based peptidomimetics which are structurally similar to amide-containing compounds. They have been prepared to improve the pharmaceutical properties such as bioactivity, target specificity, and metabolic stability of the bioactive amides.

We suggested a new way of synthesizing fluoroalkene-based peptidomimetics through 2-fluoro-2-halocyclopropylamines, which provides an effective way toward fluoroalkene-based peptidomimetics with increased functional group tolerance and possibility of convergent synthesis."


Reduction Of Nitro-Compounds By Iron Pentacarbonyl - New Approach To Drug Precursors, Alexander Sharipov, Maria Vladimirovna Galkina 2018 Moscow South-Eastern School Named after V.I. Chuikov

Reduction Of Nitro-Compounds By Iron Pentacarbonyl - New Approach To Drug Precursors, Alexander Sharipov, Maria Vladimirovna Galkina

The International Student Science Fair 2018

Reduction of nitro compounds lies at the center of most of the major areas of modern chemical industry, such as pharmacy and dye manufacturing. The precursors in these industrial processes predominantly possess multiple functional groups, including those highly susceptible to reduction by most of the currently used reducing agents. Therefore, the non-selective methods of reduction of precursors result in the loss of such functional groups. Furthermore, common reducing agents can potentially trigger the undesired intramolecular interactions between the substrate molecules and in turn make it impossible to obtain the end product. The rising demand for a cheap and efficient approach ...


Rearrangements Of Fluorinated Cyclopropylamines As A Novel Approach Toward Fluoroalkene-Based Peptidomimetics, Igor Mezentsev, Vera Zaborova 2018 Moscow South-Eastern School named after V.I.Chiukov (former Moscow Chemical Lyceum)

Rearrangements Of Fluorinated Cyclopropylamines As A Novel Approach Toward Fluoroalkene-Based Peptidomimetics, Igor Mezentsev, Vera Zaborova

The International Student Science Fair 2018

Organofluorine molecules have been widely applied in various research fields because of the unique properties of fluorine atoms. One type of fluorinated compounds is fluoroalkene-based peptidomimetics which are structurally similar to amide-containing compounds. They have been prepared to improve the pharmaceutical properties such as bioactivity, target specificity, and metabolic stability of the bioactive amides.

We suggested a new way of synthesizing fluoroalkene-based peptidomimetics through 2-fluoro-2-halocyclopropylamines, which provides an effective way toward fluoroalkene-based peptidomimetics with increased functional group tolerance and possibility of convergent synthesis.


Steric Effects Of Alkyl Ammonium Salts On The Combustion Of Exchanged Smectite Clays, Celeste A. Keith 2018 Stephen F. Austin State University

Steric Effects Of Alkyl Ammonium Salts On The Combustion Of Exchanged Smectite Clays, Celeste A. Keith

Electronic Theses and Dissertations

Bomb calorimetry was explored as a new method for determining the cation exchange capacity (CEC) of clays. Smectite clays were modified with several alkyl ammonium salts varying in number of carbons and the spatial orientation of the carbons about the central nitrogen atom. The clays used, standards purchased from the Source Clay Repository, have CECs of 44, 80, 88, and 120 meq/100 g. Theoretically, the combustion energy of the organo-clays should be approximately the same for each salt. Any differences in energy would be due to the different structures of the salts and how they are oriented in the ...


Oxidation Of N-Doped Multiwalled Carbon Nanotubes And Formation Of Discontinuous Spiraled Carbon Nanoribbons, Aman Preet Kaur, Mark S. Meier, Rodney Andrews, Dali Qian 2018 University of Kentucky

Oxidation Of N-Doped Multiwalled Carbon Nanotubes And Formation Of Discontinuous Spiraled Carbon Nanoribbons, Aman Preet Kaur, Mark S. Meier, Rodney Andrews, Dali Qian

Chemistry Faculty Publications

The effects of five commonly used wet chemical oxidations were studied for the extent of oxidation of graphitized nitrogen-doped multiwalled carbon nanotubes (N-MWCNTs). KMnO4/ H2SO4 was the most potent oxidant, as it produced the highest fraction of oxygen-containing functional groups. Electron microscopy studies showed that the treatment of annealed N-MWCNTs (G-N-MWCNTs) with H2SO4/HNO3 and H2SO4/KMnO4 mixtures leads to interesting spiraled ribbon textures. A structural model, involving the stacking of coiled subunits to form a discontinuous carbon nanoribbon rather than a continuous ribbon is proposed to explain ...


Total Synthesis Of (±)-Isodihydrokoumine, (±)-(19z)-Taberpsychine, And (±)-Isodihydroukoumine N4 Oxide, Jeff Kerkovius 2018 The University of Western Ontario

Total Synthesis Of (±)-Isodihydrokoumine, (±)-(19z)-Taberpsychine, And (±)-Isodihydroukoumine N4 Oxide, Jeff Kerkovius

Electronic Thesis and Dissertation Repository

We report the total synthesis of the natural products (±)-isodihydrokoumine, and (±)-(19Z)-taberpsychine in 11 steps each, and (±)-isodihydrokoumine N4-oxide in 12 steps from commercially available starting materials. The key reactions include an intramolecular [3+2] nitrone cycloaddition, and Lewis acid mediated cyclizations of a common intermediate to provide the core structures of either (19Z)-taberpsychine or isodihydrokoumine. Both failed and successful routes will be discussed.


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