Atmospheric fine particulate matter (PM2.5) has been linked to the death of 7 million people per year around the planet. The organic portion of PM2.5 is responsible for increases in oxidative stress, inflammation, mutation and carcinogenesis. Anthropogenic activity releases more organic material into the atmosphere, and has increased the amount...
Metal-oxo clusters can be described as soluble pieces of metal-oxide frameworks. Currently, metal-oxo clusters are being considered as solution-based precursors for extreme ultraviolet (EUV, 13.5 nm) photoresist materials, which are a crucial component in the fabrication of microelectronic devices. Two different photoresist precursor systems have been investigated – alkyltin clusters...
With the rise of resistant bacterial pathogens, currently prescribed antibiotics are rendered useless. In recent years, marine natural products (MNPs) have emerged as novel sources for drug leads. The ocean is a complex environment where marine animals cohabitate with many, and sometimes harmful microorganisms and viruses, but resist infections. Developed...
Metal-oxo clusters are discrete molecular metal-oxides. Most metals form numerous cluster compounds that can be ligated, unligated, charged or neutral, controlling their solubility in water and/or organic solvents. They are important species to study reaction pathways from the monomeric building units to the bulk metal oxides, and have many application...
Dental plaque is one of the well-characterized biofilms in the human body. Oral bacterial species play vital roles in maintaining healthy bacterial homeostasis as well as causing oral infections. Many of the oral diseases are caused by opportunistic pathogens, and therefore, the bacterial metabolic activities become important in dictating their...
Coded metrics that compare representations of structures within the human body to evaluate their similarity are considered useful for planning radiation therapy on cancer targets. However, existing metrics fail to take into account the dose of radiation that will be received by both the target, and surrounding non-target tissue, during...
Fungi have long been used for discovery of new chemical scaffolds. In the clinical setting, the fungal natural products penicillin, statins, and cyclosporine have revolutionized medicine to treat diseases and infections. In the environment, fungal natural products have been used as herbicides, fungicides, and insecticides to protect crops, livestock, and...
This study aimed to explore the relationship between urinary cortisol levels and proximity-seeking behavior in shelter cats and the impact of socialization programs on these two factors. A Spearman’s correlation test found no correlation between cortisol levels and proximity-seeking behavior in shelter cats. Fisher’s 2x2 tests confirmed that the changes...
Traffic exhaust is an important source of air pollution. This exposure assessment study examined traffic related air pollution in Curitiba, Brazil, and is particularly relevant due to 75% of the population using diesel public transportation. Traffic density was tabulated, and vehicle-type was distinguished based on their fuel type (diesel or...
Tethering fluorophores on metal nanoparticles for metal enhanced fluorescence (MEF) has attracted a lot of attention from scientists interested in fluorescence based approaches. MEF has many benefits in fluorescence related techniques, because the analytical signal increases and enables potentially lower detection limits or better sensitivity. Many types of nanoparticles have...
Mandelalide A has attracted considerable interest from the synthetic community due to its intriguing structure and important cytotoxic activity. Madeirolide A, a structurally related macrolide, shows promising antifungal activity but no appreciable anticancer activity. This dissertation describes synthetic studies toward mandelalide A, madeirolide A and their hybrid structures.
Part I...
Analytical techniques are utilized in a wide variety of applications. Traditionally, analytical measurements are achieved by trained personnel in a laboratory setting using expensive scientific instruments, which limits their applicability in resource-limited areas and point-of-care applications. Therefore, the concept of enabling these laboratory-based qualitative and quantitative assays in microfluidic device...
My work has focused on streamlining the study of organic compound structure, properties, and reactions by 1) understanding and using available computational software, 2) developing software packages to facilitate data manipulation as well as augment public programs, and 3) applying public and in-house developed software to further the understanding of...
Dearomatization reactions exist broadly in biosynthesis and chemical synthesis. The highly functionalized atoms of arenes can be masked by it aromaticity, and upon dearomatization, those reactive atoms can be readily applied to bond formation and further manipulation. The total synthesis of (–)-cephalotaxine and (–)- homoharringtonine is described via an oxidative...
In this dissertation, I describe the experimental investigation of large superfluid helium droplets. The goal and direction of this thesis is to facilitate the use of these droplets as part of our project ss-EDI. The overall scheme of ss-EDI is to dope proteins inside helium droplets and collect a diffraction...
In this dissertation, the process of computational modeling of amorphous oxide materials is studied. Amorphous oxides have random atomic arrangements with no long-range structural order which makes it difficult to study structure-property relationships. Despite the difficulties, amorphous oxides have great uses as semiconductors and dielectrics in thin-film transistors. The ability...
Aqueous film forming foams (AFFFs) are proprietary mixtures containing hydrocarbon surfactants and per-and polyfluoroalkyl substances (PFASs) that are used to extinguish hydrocarbon-based fuel fires. There is limited information on hydrocarbon surfactants in AFFFs and AFFF-contaminated groundwater even though they are more abundant (5-10% w/w) than PFASs (0.9-1.5% w /w) in...
This dissertation is separated into two parts according to the two major distinct research projects. In Part I, the full account of synthetic studies toward C10-functionalized lycopodium alkaloids is described. In Part II, the detailed discussion on the exploration of the Pummerer cyclization methodology and its application to the total...
Part I of this dissertation includes the chronological synthetic background of mandelalide A as well as the synthesis of the C1-C14 glycosylated southern subunit of mandelalide. A key aspect of the synthesis includes a novel silver-catalyzed cyclization (AgCC) of a propargylic benzoate to construct the substituted cis-pyran ring system present...
Small molecule drugs have been instrumental in our fight against diseases, beginning when some of the earliest ancient cultures used plant remedies to treat illnesses. More recently, the skill of isolating and characterizing the active ingredients within bioactive plants and microbial extracts has led to the isolation and design of...
Exploring bioactive natural products has contributed largely to clinically approved drugs we have been using over the last 100 years. Especially among the anti-infective drugs, around 70% of currently used antibiotics were discovered or derived from microbial secondary metabolites, among them compounds like vancomycin, chloramphenicol, and erythromycin. Facing the unavoidable...
This work investigates the effect of cation substitution on the properties of the lead-free, solid solution (Na₀.₅Bi₀.₅)TiO₃-BaTiO₃ (NBT-BT). Substitution into NBT-BT increases disorder and increases the relaxor ferroelectric properties. These relaxor ferroelectric materials show large piezoelectric strains that can be utilized in actuator applications. Ceramic samples were prepared using standard...
In this dissertation, the structure and electronic properties of multiple metal oxide thin films are characterized and presented. Prompt inorganic condensation (PIC) of metal-oxo and –hydroxo clusters was evaluated as a technique for making metal oxide clusters in two separate studies. The first focuses on the synthesis of lithium niobate...
Water is an absolute necessity for life as we know it. It provides a useful medium in which chemical reactions take place that allowed for the development of single cellular organisms. When combined with the evolutionary accident that was pho- tosynthesis, water became not only a useful medium chemical reactions,...
Structure-property relationships have always underpinned the field of solid state chemistry; dependable structural descriptions are integral to understanding and controlling the physical properties of inorganic compounds old and new. While a handful of crystal structures are celebrated for their versatility, flexibility, and functionality, the existence of more exotic structures is...
Recently researchers have discovered that groups of small non-coding RNAs (ncRNAs) play regulatory roles in gene expression and participate in various biological processes. For example, pathogenesis of many diseases, cell cycle regulation, and signaling pathways. Intracellular and live cell imaging of small ncRNA groups will reveal their relative expression levels...
Mass Spectrometry has emerged as an analytical core technique in omics sciences, in particularly mass spectrometry has advanced the fields of proteomics, metabolomics and lipidomics in recent years. Mass spectrometric techniques have enabled the characterization and determination of abundance levels of a wide range of biomolecules at molecular and system-wide...
Mensacarcin is a stereogenic complex polyketide with potent anti-tumor activity produced by a soil-dwelling Streptomyces bottropensis. The US National Cancer Institute (NCI) 60 human tumor cell line anticancer drug screen (NCI-60) reveals mensacarcin’s cytostatic properties in almost all tested cell lines and distinct cytotoxic properties specifically in eight melanoma cell...
The furanyl diterpenoid family of natural products has drawn the attention of both synthetic organic chemists and pharmacologists due to their complex structural architectures and diverse biological activity. Among them, wortmannin has been most extensively studied for biological activities. All these furanyl diterpenoids consist of a highly strained naptha[1,8-bc]furan core,...
Pharmaceuticals, molecular catalysts, and secondary metabolites often contain nitrogen. The problems faced synthesizing compounds which contain nitrogen was because of the Lewis base reactivity of nitrogen lone pairs, and the acidic protons of some nitrogenous functional groups. We developed two methods for the synthesis of nitrogeous compounds. Additionally, we successfully...
Widespread installation of renewable energy sources, such as wind and solar, has been delayed by the lack of suitable stationary energy storage solutions. Current large-scale technologies, such as pumped hydro and compressed air, are geographically restricted. This is where electrochemical energy storage - batteries or hybrid capacitors can play a...
Grid-scale energy storage systems are urgently needed to increase the flexibility and rigidity of the grid for modern society and take full advantage of the renewable green energy resources such as solar energy and wind energy. Na-ion batteries (NIBs) and K-ion batteries (KIBs) have been emerged as one of the...
Frontier research of non-aqueous actinide clusters is discussed. Since the inception of the uranyl peroxide clusters over the last decade, they have only been synthesized and characterized as solid crystals and in aqueous solution. This thesis provides thorough characterization of aqueous uranyl clusters and the first demonstration of uranyl cluster...
My work has focused on investigating synthetic organic reactions using applied computational methods. Non-covalent interactions are critical to catalysis, mechanism, and stereoselectivity, with the most prominent interaction for isothioureas being the S···O contact between the catalyst sulfur atom and the oxygen of the acyl group. A comprehensive joint experimental and...
Fungi have long been a prolific source of clinically approved drugs. The antibiotic penicillin, the cholesterol lowering statins, and the immunosuppressant cyclosporine have changed the treatment of human diseases in the last century. Recently, genome analysis of filamentous fungi has revealed that the biosynthetic potential for natural product expression is...
Natural products from plants, bacteria, and fungi play an important role in society. Over the last 35 years, natural products and their derivatives have inspired over 60% of all FDA approved small-molecule drugs, and are among the top prescribed therapeutics.1-2 Fleming’s discovery of the fungal antibiotic penicillin started the “Golden...
High-resolution mass spectrometry was used to measure a range of volatile organic compounds (VOCs) in real time as they were produced by the ubiquitous marine cyanobacterium Synechococcus WH8102 during a 24-hour light/dark cycle. Ethenone, acetaldehyde, ethanol, isoprene, acetic acid, dimethyl sulfide (DMS), acetone, phenol, and several as-yet unidentified compounds were...
Tuberculosis (TB) is a pressing global health issue with approximately one third of the world’s population infected by this bacterium. As one of the most dangerous infectious diseases, it has killed approximately 1.7 million people of all ages around the world per year (World Health Organization, 2016). Currently, several drugs...
A method was developed to quantify organochlorine pesticides in whale scat. This method would ideally replace analysis of pesticides in blood and tissue samples, which are difficult to acquire. Scat samples were collected from one stranded gray whale and three live whales. The samples were extracted with pressurized liquid extraction,...
The synthesis of superheavy element evaporation residues is described by the product of the capture cross section, fusion probability, and survival probability. Capture cross sections are moderately well known. The fusion probability is the least known with many uncertainties. The formalism for the survival probability is known, but the parameters...
Two perovskite materials (Bi0.5(A)0.5)(Sc0.5Nb0.5)O3, where A = K+ and Na+ were synthesized phase pure for the first time. Their structures were determined by indexing synchrotron X-ray diffraction data and subsequent combined Rietveld refinement on neutron and synchrotron X-ray diffraction data revealing significant disorder on the A-sites of these materials. A...
Iron oxide materials including ferrihydrite and magnetite play essential roles in contaminant transport, pH control of surface and groundwater, and microbial activity. They have various applications ranging from data storage to cancer therapy. Recent studies showed that the NPs growth does not involve atom by atom nucleation but starts by...
Inorganic structures play an important role in materials due to their versatility and diversity. A complete understanding of the structure of a material is vital to enhance the creation of new materials that fill voids in research. The rational design of these compounds is driven by the exploitation of structure-property...
The general theme of this dissertation is the application of novel carbon based micro sensors with the scanning electrochemical microscopy (SECM). SECM allows positioning of the probe without touching the substrate while mapping the chemical parameters in 3D space above the substrate. The main focus of the dissertation is the...
Polyoxometalates are discrete anionic oxo clusters of the Group V and VI transition metals that can be conceptualized as molecular metal oxides. Because they are pairable with any alkali cation, a great deal of fundamental chemistry can be gleaned from their study, including solubility trends and insight into cation binding...
Nanostars have many potential applications, particularly in biomedicine, such as drug delivery, detection assays, and even cancer treatment. Seeing how their plasmon changes in response to changes to the environment of the nanostars can give us an insight to the stability of the nanostars. Our current studies involve the effect...
The post-emission total kinetic energy release (TKE) in the neutron induced fission of ²³²Th was measured (using white spectrum neutrons from LANSCE) for neutron energies from En = 3 to 91 MeV. In this energy range the average post-neutron total kinetic energy release decreases from 162.3 ± 0.3 at En...
State-of-the-art, high-resolution mass spectrometry techniques for acquisition of metabolomic and lipidomic data coupled with advanced computational methods provide new opportunities for interpreting large and complex datasets and comprehending the underlying biological processes of diseases. Both metabolomics and lipidomics strive to obtain comprehensive analyses of small molecules, i.e., metabolites and lipids,...
The solution chemistry and kinetic behavior of hafnium peroxy sulfate solutions ("HafSOx") is described in terms of peroxide content and solution speciation. Additionally, thin film behavior, including thermal behavior and solubility, is characterized, and a mechanism of patterning is presented, as well as parameters that should be considered when looking...
Polycyclic aromatic hydrocarbons (PAHs) are environmental contaminants produced mainly from the incomplete combustion and pyrolysis of organic matter. PAHs are among the major contaminants at over 800 Superfund sites, nationwide. Thermal remediation is used as a method to remediate soils contaminated with PAHs through the use of heat to mobilize...
Femtosecond stimulated Raman spectroscopy (FSRS) is a powerful ultrafast technique which can track photoinduced excited state structural events on femtosecond (fs) to picosecond (ps) timescales. In addition to high temporal and spectral resolutions, FSRS provides a broad spectral window from ca. 100—2000 cm-1 for detection, enabling the direct mapping of...
Pactamycin, first reported in 1962, is a potent antitumor antibiotic produced by the soil bacterium Streptomyces pactum. Structurally, it contains a cyclopentitol core unit, a 3-aminoacetophenone (3AAP), a 6-methylsalicylic acid (6-MSA), and a N,N-dimethyl urea. The aminocyclopentitol ring is derived from glucose, possibly via N-acetyl glucosamine (GlcNAc), the 3-aminoacetophenone (3AAP)...
Femtosecond stimulated Raman spectroscopy (FSRS) is an ultrafast vibrational technique which allows rapid collection of Raman spectra with simultaneously high temporal and spectral resolution. With the recent development of FSRS methodology, three FSRS techniques (conventional, tunable, and anti-Stokes) have been implemented in our laboratory to dissect the excited state structural...
The physical properties of hydrochloric acid and deuterium chloride were derived through the use of the harmonic oscillator and rigid rotor quantum mechanical models. By first obtaining angular momentum quantum values for HCl and DCl through Fourier Transform Infrared Spectroscopy, these two systems could be summed and processed with additional...
Novel donor-typed ternary graphite intercalation compounds (GICs) are synthesized and characterized containing (1) pyrrolidinium cations with DMSO co-intercalates; (2) alkali metal cations with crown ether co-intercalates; and (3) alkali metal cations with polyethylene glycol co-intercalates. Structural and compositional data are obtained for the stable products. A new ether-amine co-intercalate exchange...
The first part of this manuscript is about the total synthesis of the Arundo donax bis(indole) natural products. The A. donax alkaloids were prepared using the first example of an ynindole Diels–Alder reaction. Each were then separated, isolated, and determined to have stable enantiomeric conformations at room temperature (Chen, J.;...
Electrochemical capacitors and batteries are two major electrochemical energy storage technologies, which have been investigated extensively to meet the rapidly-growing demand for higher energy, higher power, lower cost and enhanced safety in the past few decades. With the charge storage mechanism of electrostatic charge adsorption desorption via electrical double layers,...
Polycyclic aromatic hydrocarbons (PAHs) are a group of environmental contaminants consisting of fused benzene rings. Parent-PAHs, methylated-PAHs (MPAHs), and PAHs with molecular weight of 302 a.m.u (MW302-PAHs) are considered as unsubstituted-PAHs. These unsubstituted-PAHs undergo transformation reactions resulting in the formation of PAH-transformation products (PAH-TPs), or substituted-PAHs, including nitrated-, oxygenated-, and...
This thesis is separated into three distinct projects. First, synthetic studies towards the furanosteroid viridin shown in part I. Second, synthetic studies towards the diperene obtusanal shown in part II. Third, the analysis, characterization, and synthesis of coronene derivatives towards their application in organic batteries shown in part III. Significant...
Pyroprocessing is an advanced technology for recycling used nuclear fuel. Pyrochemical processes encompass a wide range of chemical, physical, and electrochemical methods to partition fission products and other components from used nuclear fuel, which allows for the reuse of the actinides in nuclear fuel. This dissertation investigates two chemical systems...
In this dissertation, the spectroscopic properties and thermodynamic stability of a class of materials known as metal oxo and hydroxo clusters are studied. In aqueous solutions, many metals can aggregate into discrete clusters of metals bridged by oxo or hydroxo ligands. These clusters are of particular interest to us for...
Fluorescence has proven to be a robust and powerful method of analysis in numerous fields: forensics, pharmaceutics, geology, food science, and environmental sciences have all developed a large collection of fluorescence instruments and methods to overcome application-specific challenges. Biological applications saw the same development of a fluorescence toolkit with methods...
Oxo-hydroxo Group 5 metal clusters are an untapped resource to study and advance aqueous solution processing of metal oxide thin films. The tetramethylammonium (TMA) hexatantalate salt (TMA6[H2Ta6O19]) yields dense Ta2O5 films (~95% of the bulk ß-Ta2O5 density) with atomically smooth surfaces (<4 Å root mean square surface roughness). This same...
Aqueous hydroxo Hf nanoclusters enable studies to identify and codify steps in the deposition of Hf-based oxide thin films from solution precursors. HfOCl2 reacts with combinations of H2O2(aq), acids, and TMAH to produce polymetal species at high pH and low pH. X-ray scattering and spectroscopic methods reveal the nature of...
Phosphate and peroxide stabilize new oxo-hydroxo niobium clusters in water at low pH. The clusters open a new chapter in aqueous niobium chemistry under acidic conditions. The clusters also produce atomically smooth, amorphous niobium oxide phosphate (NbPOx) thin films. Reaction pathways from cluster solutions to amorphous niobium oxide phosphate solids...
Chemistry of preparing dense film from solution deposition is explored with several cases in this thesis. Surface dense structure, conversion at melting point, and ion exchange in aqueous solution are the main topics covered here for the thin films of aluminum oxide phosphate and tin dioxide. Thin film density, optical...
Recent experiments have advanced the current understanding of multi-nucleon transfer(MNT) reactions. Within nuclear science, most nuclear reaction experiments consist of a stationary target material, that is then bombarded by a moving projectile. Overall nuclear reactions can be used to produce a desired isotope. In the case of this particular study...
We have developed a 100 m diameter solid-state potentiometric pH sensor to study the bacterial metabolism at the biofilm-biomaterial interface in real-time. The newly developed agar-coated pH sensor is both highly resistant to biofouling and stable, with a drift of 1 mV/h in physiological conditions. We used multiwall carbon nanotubes...
In this dissertation, I describe the experimental investigation in electron diffraction of molecules in superfluid helium droplets. The project is part of an overall scheme called ‘single molecule serial electron diffraction imaging’ (SS-EDI), with the ultimate goal of building an apparatus to determine atomic structures from oriented macromolecules. In SS-EDI,...
One post-transcriptional mechanism that regulates the progression of cancer and other diseases involves small 22-23 nucleotide sequences called microRNA (miR). Early detection of small changes in concentration of these biomarkers holds potential to diagnose diseases at their earliest stages. Use of current nucleic-acid based biosensors, like molecular beacons, for in...
In Part I, (4S,5R)-4,5-dimethyl-4-phenylcyclohex-2-enone (19a) was prepared in 73% yield with high enantio- and diastereo-selectivity (er > 98:2, dr > 20:1) on a multigram scale by a Yamada-Otani condensation between (E)-pent-3-en-2-one and 2-phenylpropanal catalyzed by a sulfonimide derivative of (S)-proline (18, HuaCat®). Synthetically useful transformations of the cyclohexenone product 19a...
Amorphous metal thin films lack the grain boundaries and dislocations present in
crystalline metal films. As a result, amorphous metal films can be more mechanically robust, atomically smooth, and more resistant to chemical attack than crystalline metals. However, amorphous metals are meta-stable and subject to crystallization upon heating, thus limiting...
Miniaturized and portable microfluidic analytical platforms have been widely explored in the broad field of chemical analysis. The concept of microfluidics offer a number of important advantages, including low reagent consumption, low-cost detection, high sample throughput, and shorter analysis time. Semiconductor nanocrystals or quantum dots have been extensively utilized in...
Analytical chemistry is an area of chemistry primarily focused on the study and use of instruments for separation, identification, and quantification of an analyte of interest. Specifically, separation science within analytical chemistry often refers to the process of dividing mixtures into their small component parts based on differences in their...
As scientists, we have an affinity for order: repeating crystal structures, Euclidean space, continuous functions… Even concepts such as defects are discussed in the context of distracting from order. Things are most logical and best described in straightforward, taxonomical fashion. But what happens when the very application desired is dependent...
Due to the high cost of precursor materials, complex oxides of 4d and 5d transition metals are under-studied compared to their 3d counterparts. Recent studies have shown that oxides containing heavier transition metals can exhibit exotic electronic states due to presence of strong spin-orbit coupling. The goal of this dissertation...
The results of the research presented in this work are related to synthesis and investigations of novel color inorganic pigments having various structures and shades. Inorganic pigments play a major role in contemporary life. They are used in paints, rubber, plastic, cosmetics etc. Searching for new, stable, environmentally benign and...
Iodine-129 is a key risk driver at sites where nuclear materials have been fabricated or processed, and it is a predominant isotope of concern in long-term waste storage strategies. I-129 exists primarily as iodate in the subsurface at the Hanford Site in south-central Washington State. Between 15 and 40% of...
Public attention and concern about per- and polyfluoroalkyl substances (PFASs) are increasing due to detection of PFASs in drinking water supplies, the environment, including remote locations, and wildlife and to the lowering of the federal health advisory levels of perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA) in drinking water. Aqueous film-forming...
In this dissertation, excited state proton transfer (ESPT) and its inhibition in solution and protein environments are revealed using both femtosecond transient absorption (fs-TA) spectroscopy and femtosecond stimulated Raman spectroscopy (FSRS). Using a tunable Raman pump to enhance transient vibrational features of the photoacidic chromophore HPTS in methanol and methanol...
Porous carbon is indispensable in modern technology applications. It is used for energy storage, gas separation, water purification, catalyst support, and chromatography. The diversity of its applications stems from its unique properties, including high specific surface area, tunable pore volume, and chemical stability. Specifically, the large surface area provides high...
The overall concept of reducing laboratory operations to a scale that fits on a single microfluidic chip has been an attractive area of research over the last several decades. Despite a surge in research, few commercial success stories have been written. Lab-on-a-chip technologies have the capability to be cost effective...
Polyoxometalates are a rapidly growing class of discrete metal oxide clusters with a wide range of applications including functional materials. These anionic clusters of the group V and VI transition metals are inexpensive and non-toxic. Within group V polyoxometalates, niobium and tantalum chemistry has been underdeveloped owing to their unique...
Three distinct methods to achieve the stereoselective synthesis of carbon-carbon bonds were investigated, encompassing: (i) the formation of axially chiral biaryl molecules by enantioselective Suzuki cross-coupling, (ii) the synthesis of α-phenylalkylboronic esters by enantioselective chain extension, and (iii) the stereospecific synthesis of alkenes by eliminative cross-coupling of enantioenriched sp³-hybridized carbenoids....
Enantioenriched sp³-hybridized carbenoid reagents CR1R2MX (X = nucleofuge, M = electrofuge) of different types were investigated for the synthesis of polysubstituted alkyl chains by iterative stereospecific reagent-controlled homologation (StReCH) and for the stereospecific connective synthesis of alkenes by eliminative cross-coupling.
In the first part, putative enantioenriched α-chloroalkyllithiums (CHRLiCl) were employed...
Gold nanostars are a relative newcomer to the nanoparticle scene, and their unique properties make them very desirable for spectroscopic applications. These nanoparticles, with their sharp tips, create electric field enhancements that interact with light in an advantageous way. This Thesis outlines our in-depth study of gold nanostar synthesis, the...
Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous contaminants formed from the incomplete combustion of organic material. These contaminants are of concern because of their widespread presence in the environment and toxic properties. In addition, PAHs encompass a class of diverse compounds with varying physicochemical properties and exist in the environment as...
This thesis is the transformation of Book IV of Milton’s epic poem Paradise Lost into graphic novel format. Transforming Milton’s epic Paradise Lost into a graphic novel offers the advantages of making the material more accessible for students, and easier to understand. The aim is to make the poem more...
In this Dissertation, the mechanism and stereomechanics of complex organocatalysis and reaction processes are disclosed. The technologies and protocols currently being developed and utilized to efficiently investigate these systems using theory are highlighted.
A detailed computational study of peptide-catalyzed acylations is disclosed. In particular, the magnitude of all possible non-bonding...
In this report, three studies are presented that aid in the development of drug discovery and their synthesis. In each, the importance of the marriage between computations and experiments is highlighted. Continued efforts in this vein are essential for future efforts towards improving human health.
The first case study investigated...
The Disney Princesses are some of the most beloved and well-recognized characters in animation across the globe. Most of these characters sing throughout their movie. This essay analyzes what I refer to as the “I Want” song of several Disney Princesses. It is divided into three sections, one for each...
In the United States, falls are the leading cause of fractures and accidental death in the elderly; 70% of these fractures are women. Hispanic women account for a large population in the US, however data on falls and fractures for these women is lacking. The purpose of this systematic review...
Tacrolimus is an immunosuppressant drug approved by the FDA for the prevention of organ transplant rejection. However, the use of this drug is hindered by its narrow therapeutic window and extreme insolubility in water. Due to these properties, the currently used tacrolimus preparations must be administered once or twice daily...
Perdeutero-spiropentane (C₅D₈) has been synthesized and infrared and Raman spectra are reported for the first time. Wavenumber assignments are made for most of the fundamental vibrational modes. Gas phase infrared spectra were recorded at a resolution (0.002 cm⁻¹) sufficient to resolve individual rovibrational lines and show evidence of strong Coriolis...
Oxidative stress is defined as an imbalance that favors the production of reactive oxygen species (ROS) over an organism's antioxidant defense. ROS have the ability to damage, either directly or indirectly, biomolecules including DNA, proteins, carbohydrates, and lipids. Various pathological conditions and environmental and chronic diseases have been associated with...
This study was conducted to assess whether healthy adults compared with those with Metabolic Syndrome (MetS) have different mean oxidative-reductive potentials. Static oxidation-reduction potentials and capacity oxidation reduction potentials (sORP and cORP, respectively) were measured in plasma samples. The RedoxSYS® measures sORP in millivolts (mV), which is proportional to the...
There has been a tremendous growth in interest in carbon nanodots (C-dots) in the past several years. As a nascent nanomaterial, C-dots have shown great promise in applications that benefit from their superior water dispersibility, low toxicity, non-blinking fluorescent output, chemical and biological compatibility, ease of functionalization and resistance to...
In this dissertation, I describe the experimental investigation of catching ions in superfluid helium droplets. The ultimate goal of our project is to build a coherent electron diffraction apparatus for atomic structure determination from oriented single macromolecules. This involves generating protein ions from electrospray ionization (ESI) and doping them in...