Chemistry Commons^™

Synthesis Of Trisubstituted Indolizines From 2-Propargyloxypyridines, Colin T. Hartgerink, Jaimie E. Van De Burg, Carolyn E. Anderson

Summer Research

• Indolizines are a versatile heterocyclic core that occurs frequently in pharmaceutical leads for a variety of indications, including: anti-bacterial1 and anti-tumor agents,2 and targets for the treatment of Alzheimer’s disease,3 asthma,4 erectile dysfunction,5 and inflammation related to respiratory or cardiovascular disease.
• While evaluating the scope of a Au(I)-catalyzed rearrangement of 2- propargyloxypyridine 1, 7 substituted indolizine 4 was discovered as an unexpected by-product (Scheme 1). The structure of indolizine 4 was confirmed by NMR and Xray analysis. Investigations revealed that acetophenone, originally present as an impurity in the reaction, is a key reagent. The use of acetophenone as the solvent, …

Harnessing The Reactivity Of The N-Methyl Diaminobenzoyl Linker To Access C-Terminally Modified And Macrocyclic Peptides, Christine Arbour

Wayne State University Dissertations

This thesis describes the exploration of accessing C-terminally modified and macrocyclic peptides through N-acyl urea (MeNbz) displacement. Prior to this work, the diaminobenzoyl linker was used to access thioesters for native chemical ligation. Only solution-phase displacement of the N-acyl urea with thiol nucleophiles was previously reported.

The N-Me-diaminobenzoyl (MeDbz) linker was initially used to access C-terminal glycine esters, amides, and acids from a single peptide substrate. This led to the total synthesis of Conopressin G and two analogs. The propensity of the C-terminal cysteine residue to undergo epimerization was investigated using this strategy. After optimization, C-terminal cysteine esters, amides, and …

Influence Of Side Chain Conformation On The Mechanism(S) Of Glycosylation Reactions; Investigation Of Sialidation Reaction Mechanism(S) By Kinetic Studies, Harsha Chandhana Amarasekara

Wayne State University Dissertations

Glycosylation, being the key reaction of glycobiology and carbohydrate chemistry, demands robust and stereoselective glycosylation methods. The rational development of such methods necessitates knowledge of the glycosylation reaction mechanism and the factors influencing glycosylation reactions. The work discussed in this dissertation is focused on studying glycosylation reaction mechanisms and exploring the key factors influencing them.

Chapter one reviews the background to the research, starting with a brief introduction of the significance of carbohydrates as structural and energy-storage materials. The significance of cell surface carbohydrates and their roles in communication and related processes are discussed along with examples of their applications …

Binary And Ternary Transition Metal Pnictide Nanoparticles And Their Three-Dimensional Assemblies: Towards Promising Magnetic Refrigeration Materials, Malsha Anuradhi Hettiarachchi

Wayne State University Dissertations

BINARY AND TERNARY TRANSITION METAL PNICTIDES NANOPARTICLES AND THEIR THREE DIMENSIONAL ASSEMBLIES: TOWARDS PROMISING MAGNETIC REFRIGERATION MATERIALS

by

MALSHA ANURADHI HETTIARACHCHI

May 2019

Advisor: Dr. Stephanie L. Brock

Major : Chemistry

Degree : Doctor of Philosophy

Bulk MnAs has been recognized as a potential MR material with large MCE. However, the magnetic transition of bulk MnAs suffers from a large thermal hysteresis of 6 K precluding efficient MR cycling, and the magnetic entropy change associated with the phase transition is limited to a narrow temperature range, making the temperature control window very small. Solid solutions of MnAs, synthesized by both …

Nonadiabatic Dynamics: A Semiclassical Approach, Ruixi Wang

Wayne State University Dissertations

Nonadiabatic dynamics has been an essential part of quantum chemistry since the 1930’s. Nonadiabatic effects play a crucial role in photo-physical and photo-chemical reactions for both small and large molecules in both gas and condensed phases. Modeling dynamics of photoinduced reactions has been a new frontier of chemistry. Many dynamical phenomena, such as intersystem crossing, non-radiative relaxation, and charge energy transfer, require a nonadiabatic description which incorporates transitions between electronic states.

In Chapter 2, the property of scattering region in the semiclassical limit is investigated. We suggest that a nuclear wavepacket close enough to the conical intersection will propagate ballistically …

Facile Access To Functionalized Chiral Secondary Benzylic Boronic Esters Via Catalytic Asymmetric Hydroboration, Suman Chakrabarty, Hector Palencia, Martha D. Morton, Ryan O. Carr, James M. Takacs

James M. Takacs Publications

Allylic and homoallylic phosphonates bearing an aryl or heteroaryl substituent at the γ- or δ-position undergo rhodium-catalyzed asymmetric hydroboration by pinacolborane to give functionalized chiral secondary benzylic boronic esters in yields up to 86% and enantiomer ratios up to 99 : 1. Compared to minimally-functionalized terminal and 1,1-disubstituted vinyl arenes, there are relatively few reports of efficient catalytic asymmetric hydroboration (CAHB) of more highly functionalized internal alkenes. Phosphonate substrates bearing a variety of common heterocyclic ring systems, including furan, indole, pyrrole and thiophene derivatives, as well as those bearing basic nitrogen substituents (e.g., morpholine and pyrazine) are tolerated, …

High Initial Reversible Capacity And Long Life Of Ternary Sno2‑Co‑Carbon Nanocomposite Anodes For Lithium‑Ion Batteries, Pan Deng, Jing Yang, Shengyang Li, Tian-E Fan, Hong-Hui Wu, Yun Mou, Hui Huang, Qiaobao Zhang, Dong-Liang Peng, Baihua Qu

Department of Chemistry: Faculty Publications

The two major limitations in the application of SnO₂ for lithium-ion battery (LIB) anodes are the large volume variations of SnO₂ during repeated lithiation/delithiation processes and a large irreversible capacity loss during the first cycle, which can lead to a rapid capacity fade and unsatisfactory initial Coulombic efficiency (ICE). To overcome these limitations, we developed composites of ultrafine SnO₂ nanoparticles and in situ formed Co(CoSn) nanocrystals embedded in an N-doped carbon matrix using a Co-based metal–organic framework (ZIF-67). The formed Co additives and structural advantages of the carbon-confined SnO₂/ Co nanocomposite effectively inhibited Sn coarsening …

Generation And Reactivity Of A One-Electron Oxidized Manganese(V) Imido Complex Bearing A Macrocyclic Tetraamido Ligand, Huatian Shi, Jianhui Xie Xie, William W. Y. Lam, Wai‐Lun Man, Chi‐Keung Mak, Shek‐Man Yiu, Hung Kay Lee, Tai‐Chu Lau

Faculty of Science & Technology (THEi)

The synthesis and X‐ray structure of a new manganese(V) mesitylimido complex with a tetraamido macrocyclic ligand (TAML), [MnV(TAML)(N‐Mes)]− (1), are reported. Compound 1 is oxidized by [(p‐BrC6H4)3N]+.[SbCl6]− and the resulting MnVI species readily undergoes H‐atom transfer and nitrene transfer reactions.

General Chemistry 2, Themis Lazaridis

Open Educational Resources

No abstract provided.

Split Probe Detection Of The Influenza A Virus For Improved Diagnostics In A Point Of Care System, Tamar Yishay

Honors Undergraduate Theses

A group of Influenza viruses, RNA containing viruses of the Orthomyxoviridae family, consists of Influenza virus types A-D and has been known to cause the Flu, a respiratory illness associated with numerous detrimental symptoms that can lead to death. Influenza A virus (IAV) is constantly changing and is capable of causing pandemics. Currently used diagnostic methods include virus culturing, immunoassays including rapid influenza detection tests (RIDTs), and molecular assays including those based on RT-PCR. Most of the methods can be only performed in the certified diagnostic laboratories equipped with sophisticated instrumentation and/or special biosafety facilities. The results using these methods …

Urinalysis Screening Of Drugs In Adulterated Samples Via Direct Analysis In Real Time -- High Resolution/ Mass Spectrometry (Dart-Hr/Ms), Bianca E. Olivieri

Honors Undergraduate Theses

Current screening methods for drug analysis with urine samples includes examination of the sample with an immunoassay. These methods are used to determine the concentration of drug metabolites contained within the sample prior to further confirmatory testing. Drug testing plays a crucial role in maintaining safe workplace environments and safety of individuals. However, a positive result can lead to heavy consequences for the employee including suspension or removal from the workplace. Therefore, a majority of individuals add commonly known products into the sample to evade detection by developing a false negative result. Although specimen integrity examinations are performed to identify …

An Investigation Of Textile Fibers By Means Of Rgb Analysis Of Birefringence, Olivia F. Feild

Honors Undergraduate Theses

Fiber analysis using birefringence has been around for years but has only recently been looked at more closely under a microscope. Recent scientists have proposed methods to correct issues found with fiber analysis using birefringence, yet there has not be a defined perfect method. This research will focus on correcting previously found issues with works by Michel-Lévy and Sorensen's, as well as other scientists involved and perfecting the analysis of fiber through birefringence. The goal will be to take this research one step further into the analysis of textile fibers by RGB value analysis and birefringence. The RGB values will …

Electro- And Photocatalytic Carbon Dioxide Reduction And Thermal Isomerization Of Highly Strained Tricyclocompounds, Weiwei Yang

Electronic Theses and Dissertations

Anthracene-bridged dinuclear rhenium complexes are reported for electrocatalytic and photocatalytic carbon dioxide (CO2) reduction to carbon monoxide (CO). Related by hindered rotation of each rhenium active site to either side of the anthracene bridge cis and trans conformers have been isolated and characterized. Electrochemical studies reveal distinct mechanisms whereby the cis conformer operates via cooperative bimetallic CO2 activation and conversion and the trans conformer reduces CO2 through well-established single-site and bimolecular pathways analogous to Re(bpy)(CO)3Cl. Higher turnover frequencies are observed for the cis conformer (35.3 s−1) relative to the trans conformer (22.9 s−1) with both outperforming Re(bpy)(CO)3Cl (11.1 s−1). Photocatalytic …

Ni And Au Transition Metal Complexes In The Photocatalytic Co2 Reduction Reaction, Shakeyia Davis

Electronic Theses and Dissertations

The production of renewable fuels by the conversion of solar energy into chemical energy is a challenge. Photocatalytic and electrocatalytic conversion of CO2 to usable fuel precursors are approaches to overcoming this challenge. The two-electron reduction of carbon dioxide to carbon monoxide is an appealing process because CO can be used as a commodity chemical in industrial processes. Many molecular CO2 reduction catalysts have been reported and commonly use expensive late transition metals. These systems are inspired by natural photosynthesis and generally combine a photosensitizer, a catalyst, and a sacrificial electron donor. This work focuses nickel and gold complexes as …

The Development Of Novel Rhenium- And Copper-Based Molecular Catalysts For Applications In Energy Conversion Chemistry, Joseph Michael Lee

Electronic Theses and Dissertations

Since the Industrial Revolution, the consumption of fossil fuels has increased dramatically worldwide. The combustion of fossil fuels leads to the generation of carbon dioxide (CO2) emissions. CO2 is a greenhouse gas, but also a C1 feedstock that could be utilized for the generation of renewable fuels and commodity chemicals. However, CO2 is chemically inert and typically demands strong chemical reductants or very negative potentials before it undergoes conversion into reduced carbon products. The desire to carry out CO2 conversion in the presence of water presents a significant challenge, as protons may be reduced to hydrogen gas rather than facilitating …

Effects Of Synthetic Glyceryl Ester Additives On Cold Flow Properties Of Diesel Oil, Ruchapong Kaweewut

Chulalongkorn University Theses and Dissertations (Chula ETD)

The synthesis of solketal derivatives with some selected fatty acid (stearic acid, palmitic acid, lauric acid, myristic acid, oleic acid and linolenic acid) to glyceryl esters was conducted. All compounds were characterized by spectroscopic means. Cold flow properties of diesel oil with these glyceryl ester additives were studied in terms of pour point (PP). Glyceryl laurate was the most effective pour point decreasing at 1,000 mg/kg (DPP = 3°C). However, the blended diesel of 1,000 mg/kg glyceryl laurate could not commercialize finishing product because that was hazy diesel at room temperature. The combination of glyceryl laurate and commercial additive was …

Structural Investigations Using Theoretical Approaches : A Study Of Metal Halides, Borylenes, Phenalenyl Complexes And Σ-Hole Interactions, Supreeth Prasad

Honors Theses

The anomalous bending in the group 2 binary dihalides and the absence of this behavior in group 12 systems is well established. Their structuralpreferences contradict simple bonding models, yet they have received little to no attention in the literature. In this work, for the first time, the gas phase structuralpreferences of the groups 2 and 12 mixed (ternary) dihalides MXY (M=Be, Mg, Ca, Sr, Ba, Ra, Zn, Cd and Hg,and X, Y=F, Cl, Br, I, At) are investigated at high levels of theory. I extend a previously established softness criterion for bending to the mixed systems and I find that …

Rare-Earth-Activated Group Vi D0 Metal Oxides As Thermosensitive Phosphors, Samarage Sameera Perera

Wayne State University Dissertations

ABSTRACT

RARE-EARTH-ACTIVATED GROUP VI d0 METAL OXIDES AS

THERMOSENSITIVE PHOSPHORS

by

SAMARAGE SAMEERA PRASAD PERERA

AUGUST 2019

Advisor: Dr. Federico A. Rabuffetti

Major: Chemistry

Degree: Doctor of Philosophy

Thermosensitive phosphors are solid-state materials that demonstrate distinct dependence of luminescence emission on temperature. These materials enable optical temperature sensing in environments where conventional thermometry is not possible (e.g., gas turbines, combustion engines, surface temperature distributions). However, the design of thermosensitive phosphors that show adequate sensitivity and low thermal quenching in the intermediate temperature range (i.e., 500–1000 K) remains challenging. This challenge can be addressed by understanding how to rationally manipulate the …

Au60–: The Smallest Gold Cluster With The High-Symmetry Icosahedral Core Au13, Seema Pande, Xingao Gong, Lai-Sheng Wang, Xiao Cheng Zeng

Xiao Cheng Zeng Publications

Among coinage metal nanoclusters with 55 atoms, only Ag₅₅^– and Cu₅₅^– are the geometric magic-number clusters, as both exhibit icosahedral symmetry. Au₅₅^–, however, exhibits much lower symmetry due largely to the strong relativistic bonding effect. In this study, we collect a much larger population (>10,000 isomers) of low-energy isomers of Au₅₅^– to Au₆₀^– by using the combined density-functional theory and basin-hopping global optimization method. We also include the spin−orbit effect in the density-functional theory computation to achieve simulated photoelectron spectra in quantitative fashion. Remarkably, we uncover that the …

Quantification Of Surface Contamination On Genesis Solar Wind Samples, Martina Schmeling

Chemistry: Faculty Publications and Other Works

The Genesis mission was the only mission returning pristine solar material to Earth since the Apollo program up to date [1, 2]. Unfortunately, the return of the spacecraft on September 8, 2004 resulted in a crash landing shattering the solar wind collectors into small fragments and exposing them to desert soil and other debris at the landing site. To permit analysis of solar wind material embedded within a collector, surface cleaning is a necessity. Cleaning should remove surface contamination quantitatively, but leave the embedded solar wind intact. However, contamination varies from sample to sample and each fragment requires an individual …

Combusion And Emission Characteristics Of Abe/Ibe Diesel Blends, Kerry L. Lippold

A with Honors Projects

This honors project is a slide presentation summarizing and analyzing literature published on experimental research of bio-fuel diesel blends.

Atomic Layer Deposition (Ald) And Atomic Layer Etching (Ale) Of Thin Films: Synthesis And Characterization Of A New Class Of Ald Precursors, Ald Of Pralo3 Thin Films, And Thermal Ale Of Cobalt Metal Films, Wathsala Lakmali Iwadunna Waduge

Wayne State University Dissertations

ABSTRACT

ATOMIC LAYER DEPOSITION (ALD) AND ATOMIC LAYER ETCHING (ALE) OF THIN FILMS: SYNTHESIS AND CHARACTERIZATION OF A NEW CLASS OF ALD PRECURSORS, ALD OF PrAlO3 THIN FILMS, AND THERMAL ALE OF COBALT METAL FILMS

by

WATHSALA LAKMALI IWADUNNA WADUGE

February 2019

Advisor: Professor Charles H. Winter

Major: Chemistry (Inorganic)

Degree: Doctor of Philosophy

ALD is an attractive thin film deposition technique due to its unique self-limiting growth behavior and the ability to achieve Angstrom level thickness control. Alternative thin film deposition techniques such as CVD and PVD are unable to attain the conformal and Angstrom level film growth which …

Modification Of Bruker Amazon Etd And Solarix Mass Spectrometers Towards Infrared Multiple Photon Dissociation: Structural Characterization Of Modified Nucleosides, Lucas Ash Hamlow

Wayne State University Dissertations

Infrared ion spectroscopy has become an increasingly powerful tool for examining

the intrinsic structures of gas-phase ions. Infrared multiple photon dissociation (IRMPD)

action spectroscopy has been particularly successful. Several free electron laser (FEL)

facilities across the world have helped facilitate the growth of the IRMPD technique and

increasing interest has driven the development of more accessible IRMPD

instrumentation. The development of one such IRMPD instrumentation system is

described in this work, based around commercially available 3D quadrupole ion trap mass

spectrometers and Fourier-transform ion cyclotron resonance mass spectrometers.

The intrinsic gas-phase structures of nucleic acid monomers have been

extensively studied …

Synthesis And Study Of The Micellization Behavior Of A Dual Temperature- And Ph-Responsive Paa-B-Pnipam Block Copolymer, Ehsan Zarshenas Moghadam

Master's Theses and Doctoral Dissertations

Amphiphilic diblock copolymers are composed of hydrophilic and hydrophobic regions. When they are exposed to water, the hydrophobic blocks aggregate to form a hydrophobic core surrounded by hydrophilic regions outside to give a core-shell micelle. These micelles have many potential applications, such as a drug delivery system, surfactants, or nanoreactor. Many studies have been done to optimize the performance of these copolymers. In this thesis work, nine dual temperature- and pH-responsive poly(acrylic acid-block-N-isopropylacrylamide) (PAA-b-PNIPAM) diblock copolymers with different relative chain lengths of the hydrophobic and hydrophilic blocks were synthesized by reversible addition fragmentation chain transfer polymerization. The preliminary results showed …

A Comparison Of The Efficacy Of Newly-Synthesized Antimicrobial Polymers And A Preview Into Their Interaction With The Bacterial Cell Membrane., Kailey Christman

Williams Honors College, Honors Research Projects

Antibiotic-resistant bacteria present an obstacle for physicians and researchers. Over 35,000 people die annually in the U.S. from antibiotic-resistant infections each year. New antibiotics are being developed and studied, and natural products are screened to find potential new antibiotics. In this study, four polymer antibiotics with polyester backbones and peptide functional groups were studied with Escherichia coli and Staphylococcus aureus to determine the polymers’ efficacies on the different bacteria and compare the polymers to each other. Timed fluorescence microscopy experiments were performed to determine how long it takes the antibiotics to compromise the membrane integrity of fluorescently-labelled E. coli. …

Polymerization Of Bromoundecylacrylate And Alkylating Methylimidazole, Shuziao Li

Master's Theses and Doctoral Dissertations

Polymerized ionic liquids (PIL) generally are solids, but a few examples have been reported that also exhibit liquidity in the neighborhood of room temperature called liquid polymerized ionic liquids (LPIL). The development of a platform suitable for exploring LPIL properties based on the monomer 11-bromoundecylacrylate (AcC11Br) was reported. Poly(AcC11Br) is itself a liquid polymer and can be easily used to alkylate 1-methylimidazole to produce poly(AcC11C1ImBr-co- AcC11Br). Various reaction conditions were explored to examine how extensively 1- methylimidazole can be attached to this polymer, and the extent of alkylation is determined quantitatively by silver ion potentiometry. These polymers retain liquidity at …

Characterization Of The Histone Binding Properties Of The Epigenetic Reader Protein Uhrf2 To H3 In Phd Domain, Marisa Gilliam

Senior Honors Theses and Projects

Every cell contains the same genetic code, to have cell differentiation this genetic code needs to be regulated on what is expressed. The regulation of gene expression without altering the genetic code itself is known as epigenetics. An example of epigenetic regulation can be seen between the binding of UHRF2 and H3 histones. The purpose of this project is to determine ifD363 in UHRF2 is important for histone H3 binding. To do so, D363 was mutated to alanine, lysine or asparagine. The mutant protein was expressed, purified, and its ability to binding to H3 was tested by fluorescence polarization. Compared …

Understanding The Role Of Atg7 And Atg14 In Autophagy, Ronith Chakraborty

Senior Honors Theses and Projects

Autophagy is the process by which cytosolic components are trafficked to and degraded by the vacuole or lysosome. It plays a critical role in cellular health, aging, cancer, and neurodegenerative diseases. Atg7 and Atgl4 are enzymes required for the autophagic process in Saccharomyces cerevisiae. In this study, we hypothesized that Atg7 controls the size while Atg 14 controls the number of autophagosomes. Using western blotting, Pho8D.60 assay and transmission electron microscopy analysis, we found that Atg7 affects both the size and number of autophagosomes. In addition, we have created cells expressing various levels of Atgl4 using non-native promoters. In addition, …

N-Methyl Mesoporphyrin Ix As A Highly Selective Light-Up Probe For G-Quadruplex Dna, Ariana Yett , '21, Linda Yingqi Lin , '20, Dana Beseiso , '21, Joanne Miao , '22, Liliya A. Yatsunyk

Chemistry & Biochemistry Faculty Works

N-methyl mesoporphyrin IX (NMM) is a water-soluble, non-symmetric porphyrin with excellent optical properties and unparalleled selectivity for G-quadruplex (GQ) DNA. G-quadruplexes are non-canonical DNA structures formed by guanine-rich sequences. They are implicated in genomic stability, longevity, and cancer. The ability of NMM to selectively recognize GQ structures makes it a valuable scaffold for designing novel GQ binders. In this review, we survey the literature describing the GQ-binding properties of NMM as well as its wide utility in chemistry and biology. We start with the discovery of the GQ-binding properties of NMM and the development of NMM-binding aptamers. We then discuss …

Seven Coordinate Molybdenum And Tungsten Complexes Containing Tpm And Tpm Derivatives And The Impact Of Ligand Substitution On Nmr Chemical Shifts, Cole Seager

Undergraduate Honors Thesis Collection

A series of known and new seven coordinate molybdenum and tungsten complexes of tris(pyrazolyl)methane (Tpm) and substituted Tpm, [TpmM(CO)3X]+, have been synthesized. Depending on the identity of X, (bromo, iodo, hydrido) and the substitution of the Tpm ligand, substantial chemical shift differences are observed for the hydrogen on the central carbon of the Tpm ligand. Factors impacting the chemical shift of the hydrogen on the central carbon of the Tpm ligand, such as the electron donating ability of the Tpm ligand and the electronegativity of the additional ligand on the metal, will be discussed.