The strained carbon ring, bicyclo[1.1.1]pentane, was synthesized by a reaction between
1-(phenylsulfanyl)bicyclo[1.1.1]pentane, prepared from propellane, and Raney nickel.
Infrared spectra were recorded at a resolution of 0.0015 cm-1, a resolution significantly
better than previous measurements, 0.06 cm-1. A single fundamental band was analyzed
to determine the ground state and excited...
A Diels-Alder approach to biaryls (DAB) has been applied towards the synthesis
of highly substituted, programmable biaryl templates. Tri- and tetra-ortho-substituted
biaryls can be produced in just three to four steps from commercially available materials
utilizing the Diels-Alder [4+2] cycloaddition. The methods described herein will
illustrate the ability of mono...
We have developed a compact micro total analysis system (μTAS) to serve as a platform for in-situ spectrophotometric water quality monitoring. Individual fluidic, optical, and electrical components were designed, developed, and characterized. These components were combined in both an integrated (single lithographic “chip-based” platform) and a modular manner. The microfluidic...
The structural architecture present in marine toxin azaspiracid - 20 stereocenters, 9 rings, 3 separated spirocenters - has attracted considerable synthetic attention. Our efforts toward the synthesis of azaspiracid have led to the completion of both C₁-C₂₆ northern and C₂₇-C₄₀ southern halves. Herein, the
synthesis of southern FGHI ring system...
The experimental and theoretical bases of transient electric birefringence (TEB) and its application in a variety of nanomaterials, including Na-montmorillonite, cellulose nanocrystals (CNXL), and CdSe quantum dots (QDs) will be presented. TEB is a phenomenon attributed to the alignment of particles in response to an applied electric field and has...
Studies towards the total synthesis of (+)-Phomactin A (1), D (6), and G (9), fungal metabolites with unique molecular architecture and pronounced biological activity, are described. These studies resulted in the synthesis of advanced intermediates 354 and 356, which contain all of the carbon atoms of 1, 6 and 9....
The adduction of proteins and other biomolecules by electrophilic lipid peroxidation products such as 4-hydroxy-2-nonenal (HNE), 4-oxo-2-nonenal (ONE), malondialdehyde (MDA) or acrolein (ACR) is thought to be an initiating and/or propagating factor in the pathophysiology of several diseases such as atherosclerosis, diabetes, Alzheimer's, Parkinson's and other age-related disorders. The identification...
Oxidative stress is recognized as an important underlying factor in the
pathogenesis of many degenerative diseases as well as normal senescence. The
free radicals, reactive oxygen species (ROS) and electrophiles produced during
oxidative stress are capable of modifying nucleic acids, lipids and proteins. There
are a variety of oxidative modifications...
Effective methods for the enantiopure formation of substituted piperidine rings are significantly important due to their presence in alkaloid products. A valuable method to form these ring systems would be via an intramolecular heteroatom Michael addition from the corresponding enone or enal. Described herein is a methodolgy that has been...
Azaspiracid has generated an enormous amount of scientific interest in the fourteen years since its initial discovery. The structure contains a 6,5,6 bis-spiroketal, a [3.3.1] bicyclic ketal and a 6,5-spiroaminal linkage as key moieties. With 9 rings, 20 stereocenters and three alkenes, the azaspiracid immediately attracted the interest of the...
Massive die-offs of Bufo bufo gargarizans were observed in May 2008 in Mangwal
Gee, Korea. To find out the causes for this disaster several different elements
were examined: pH, total nitrogen, dissolved oxygen (DO), and dissolved heavy
metal, suspension, introduced species, habitat change, disease, temperature
changes, and precipitation and humidity....
The development of micro total analysis systems (µTAS), also called “lab-on-a-chip”, or microfluidic analysis systems, is presented in this dissertation. Various research areas, covering subjects from magnetic particles synthesis to novel microchip fabrication techniques, are explored to develop a lab-on-a-chip system capable of performing magnetic bead-based bioassays. These devices are...
This dissertation outlines two approaches for improving the efficiency and reducing the cost of photovoltaic energy generation. First, the structures of known binary copper and iron compounds are used to choose the promising compositions Fe₂XS₄ (X = Si, Ge), Cu₃TaQ₄ (Q = Se, Te), and BaCuQ'F (Q' = S, Se,...
This thesis consists of an autoethnography of a sexual assault survivor written using poems, journal entries, annotations, photographs and song lyrics. The ethnography is a chronological record of feelings the author experienced during the day prior to the attack and emotions she navigated during the year and a half after...
Crystals of an incongruent-melting compound, Ba₃MgSi₂O₈, were grown by the flux method and its structure was determined by single crystal X-ray diffraction methods. Ba₃MgSi₂O₈ crystallizes in trigonal space group P-3[bar]m1 with a = 5.6123(3) Å, c = 7.2667(9) Å and Z = 1. Eu²⁺ ions prefer one crystallographic Ba site...
Transition metal oxides are an important class of materials for the wide variety optical, electrical, dielectric, magnetic, and thermal properties observed. Their unique structure-property relationships allow for property tuning and often provide insight into the fundamentals of chemistry. The work in this thesis was focused on the design, synthesis and...
Used Nuclear Fuel (UNF) contains transuranic (TRU) elements and numerous fission products as a result of the uranium fission process and neutron activation that occur in commercial light water power reactors. Recent environmental and nuclear proliferation concerns have spawned the development of advanced reprocessing techniques to close the nuclear fuel...
The nuclear reaction ¹⁰⁰Mo(¹²⁴Sn,xn)[superscript 224-x]U has been carried out at E[subscript cot] of 578 MeV and 634 MeV using the facilities and equipment at the Holifield Radioactive Ion Beam Facility (HRIBF) at Oak Ridge National Laboratory (ORNL) in order to initiate the search for the inverse fission of uranium. Reference...
In this dissertation, I present electronic spectra of a few polycyclic aromatic hydrocarbons (PAHs): tetracene, pentacene, pyrene, benzo[g,h,i]perylene and benzo[a]pyrene using resonantly enhanced multiphoton ionization (REMPI) and zero kinetic energy (ZEKE) photoelectron spectroscopy. The work of tetracene and pentacene also combine a laser desorption source with a ZEKE spectrometer, demonstrating...
Gene synthesis is an important tool in molecular biology. However, the current
bench-top method of gene synthesis is a costly, time-intensive and reagent-consuming
process. Lab-on-chip technology has many benefits over current bench top methods.
Microchips consume smaller reagent volumes, are reusable and less expensive to make.
This thesis explores the...
Sulfide is an important species to measure in environmental water samples. The
spectrophotometric detection method for reduced sulfur species (sulfide) based on
generation of methylene blue was adapted to work in an apparatus utilizing microfluidic
PDMS mixing and observation cells with flow channels in the 100 μm range. The
benefits...
Part 1: A Diels-Alder Approach to the Synthesis of Novel Analogues of the Natural
Product Siamenol
Due to the prevalence of biaryl motifs in natural product synthesis, the Carter
research group has been exploring the utility of a Diels-Alder approach to biaryl
synthesis. The Diels-Alder approach involves a [4+2] cycloaddition...
Amphidinolide B₁ is one of the most potent cytotoxic compounds in the
amphidinolide family. Its bioactivity and intriguing structure has drawn
attention from synthetic chemists. Although numerous synthetic efforts toward
the total synthesis of amphidinolide B₁ have been published, it still remains an
unconquered synthetic target.
One of the unique...
The development of microfluidic devices for heavy metal extraction is presented in this dissertation. Various research areas, covering subjects from photochromic compound syntheses to microchip fabrication techniques are explored to develop microfluidic devices capable of extracting heavy metal ions from drinking water. Through integration of the beneficial characteristics of both...
Interesting rovibrational characteristics of two D_(3h) oblate symmetric top molecules were studied. Hamiltonian models for the fine rovibrational level structure of [1.1.1]propellane (propellane) were obtained for many low-lying modes. Ground state parameters (GSP) that are not exclusively K^(2n) dependent were obtained. Initially, the GSP were used in conjunction with density...
The work described herein details the synthesis and application of
biphenyls that probe the effects of hydrogen, Cl / Br, and methyl substituents
on the aryl ring of the terminal acetylenic carbon. From this work, we
successfully developed the rapid synthesis of phenyl acetylenes in 3-4 steps
from inexpensive commercially...
This thesis presents basic studies, including structural, optical and transport measurements, on novel chalcogenide powders and single crystals. BiCuOSe crystals have been synthesized for the first time. The crystal structure of BiCuOSe has been refined and the optical band gap has been measured to be 0.83eV. Crystal structure refinements of...
In a search for designed materials that mimic those found in biological systems, combining polymers with inorganic materials in sol-gel chemistry processes has gained momentum in the research world since the 1990's. This work methodically investigated the properties of several related polymer-SiO₂ hybrids prepared by a simple methodology that could...
Halogenated Polycyclic Aromatic Hydrocarbons (X-PAHs) are ubiquitous contaminants that are thought to be generated by processes such as chemical industries and incomplete combustion, including waste incineration and electronic waste (e-waste) burning. X-PAHs are a concern for environmental and human health because they are toxic, mutagenic, and are expected to be...
Dysfunction of mitochondria has been linked to aging and the pathogenesis of many degenerative diseases. Aside from their primary function in energy production, mitochondria are considered as a major source and target of reactive oxygen and nitrogen species (ROS/RNS) in cells as well. The mitochondrial thiol proteome is a subset...
Oxides of post-transition metals often show unique structures and properties due to the presence of lone pair electrons and the diffused s orbitals. The present work focuses on synthesis and characterizations of oxides containing Te, a heavy post transition metal.
New series of pyrochlore oxides of the formula Cs(M,Te)₂O₆ (M...
Benzylsuccinate (BSA), methylbenzylsuccinate (methylBSA), and ethylbenzylsuccinate (ethylBSA) are unambiguous anaerobic biotransformation products from toluene, xylenes, and ethylbenzene decay, respectively, and may be used to indicate intrinsic bioremediation is occurring at hydrocarbon-contaminated sites. In order to improve upon current methods that detect and quantify anaerobic hydrocarbon metabolites in field samples, solid-phase-extraction...
The 3-substituded indolic enamide moiety has been found in many marine compounds over the past 20 years. These indolic enamides exhibit various biological properties such as cytotoxic, anthelmintic, antimicrobial and HW-inhibitory activities. Among these indolic enamides, some are (E)-enamides, like coscinamide A and coscinamide B, others are (Z)-configuration in their...
Over the last decade, the use of highly branched macromolecules, called dendrimers, is emerging. Polyamidoamine (PAMAM) dendrimers, in particular, have attracted high interest due to their unique properties, such as well-defined size, shape, and solubility in water. Our group, as part of an interdisciplinary team, is currently working on developing...
The transport and deposition of airborne contaminants, including semivolatile
organic compounds (SOCs), to high elevation ecosystems is
recognized as a potential threat to these ecosystems. The objectives of
this research were to develop an analytical method to measure a wide
range of SOCs in high elevation lake sediment and to...
Chlorinated aliphatic hydrocarbons (CAHs) such as vinyl chloride (VC) and 1,-2 dichioroethane (DCA), are wide-spread groundwater pollutants found at many contaminated field sites around the world. Quantitative tools are needed to determine the in situ rates of VC and DCA transformation to ethene in contaminated groundwater. The objective of this...
Resonance Electron Capture Mass Spectrometry (REC-MS) is a sensitive
experimental technique for the study of gas-phase compounds with positive electron
affinity. This technique was used to study a class of compounds known as
baloetbylenes containing chlorine and bromine substitutions. Haloetbylenes are an
important class of compounds because ethylene is the...
Capillary electrophoresis as a technique has many applications in a broad range of fields including forensics, environmental analysis, and biological analysis and as a separation method for samples such as oligonucleotides, peptides, proteins, and pharmaceuticals. The research conducted herein is for the antibiotic pharmaceutical ciprofloxacin HCl and three impurities. Sample...
Two improvements to the established procedures for synthesis and response detection of ion-selective optical sensors (optodes) were introduced.
The first improvement addresses the drawback of organic dye (optode-localized chromoionophore) photobleaching. This positively impacts fluorescence response and allows for (1) direct measurement of hydrogen ion activity upon binding with the dye,...
Novel ternary graphite intercalation compounds (GICs) of alkali metal cations
and a wide variety of amines have been synthesized by one-pot chemical syntheses.
Alkali metals studied includes Li, Na and K. The families of amines employed are nalkylamines,
branched alkylamines, and different structural isomers of diamines and
polyamines. Intragallery structures...
The aqueous chemistries of two transition metal cations, Zr⁴⁺ and Nb⁵⁺, are examined and then used to develop inorganic precursor solutions. The oxides of these cations (ZrO₂ and Nb₂O₅) are deposited and characterized, and their morphological and optical properties discussed. Due to the obstacles created by niobium's aqueous chemistry, an...