Chemistry Commons^™

Vibrational Spectroscopy Of N-Methyliminodiacetic Acid (Mida)-Protected Boronate Ester: Examination Of The B-N Dative Bond, Dana N. Reinemann, Ashley M. Wright, Jonathan D. Wolfe, Gregory S. Tschumper, Nathan I. Hammer

Chemistry Faculty Research & Creative Works

N-Methyliminodiacetic acid (MIDA)-protected boronate esters are a new class of reagents that offer great promise in iterative Suzuki-Miyaura cross-coupling reactions. Compared to earlier reagents, MIDA esters are easily handled and are benchtop stable under air indefinitely. The success of this new species is tied to its unique molecular architecture. Compared to the simpler B-N containing molecules ammonia borane and trimethylamine borane, MIDA esters are much larger, and the sp3 hybridized boron atom is secured by two five membered rings, making this molecular class stable for spectroscopic study. Here, we present infrared, Raman, and surface enhanced Raman (SERS) spectra of methylboronic …

Slow Magnetic Relaxation And Electron Delocalization In An S = 9/2 Iron(Ii/Iii) Complex With Two Crystallographically Inequivalent Iron Sites, Susanta Hazra, Sujit Sasmal, Michel Fleck, Fernande Grandjean, Moulay T. Sougrati, Meenakshi Ghosh, T. David Harris, Pierre Bonville, Gary J. Long, Sasankasekhar Mohanta

Chemistry Faculty Research & Creative Works

The magnetic, electronic, and Mössbauer spectral properties of Fe ₂L(µ-OAc)₂ClO₄, 1, where L is the dianion of the tetraimino-diphenolate macrocyclic ligand, H₂L, indicate that 1 is a class III mixed valence iron(II/III) complex with an electron that is fully delocalized between two crystallographically inequivalent iron sites to yield a [Fe₂]^V cationic configuration with a S_t 9/2 ground state. Fits of the dc magnetic susceptibility between 2 and 300K and of the isofield variable-temperature magnetization of 1 yield an isotropic magnetic exchange parameter, J, of -32(2) cm^-1 for an …

Spectroscopic And Computational Insight Into Weak Noncovalent Interactions In Crystalline Pyrimidine, Ashley M. Wright, Lynn V. Joe, Austin A. Howard, Gregory S. Tschumper, Nathan I. Hammer

Chemistry Faculty Research & Creative Works

Effects of weak C-H⋯N interactions on the vibrational spectrum of crystalline pyrimidine are studied using Raman spectroscopy and electronic structure computations. When pyrimidine transitions from the liquid to solid state, peaks in the Raman spectrum exhibit non-uniform shifts. Calculations performed on a cluster of nine pyrimidine molecules (one pyrimidine molecule embedded in a field of its eight nearest neighbors in the crystalline geometry) predict that modes involving the movement of hydrogen atoms are associated with the observed shifts. Assignments of fundamentals and combination bands in both the liquid and solid states are also revised in the complicated C-H stretching region. …

Investigation Of Occurrence, Elimination And Degradation Of Pharmaceutical And Personal Care Products In Drinking Water Using Liquid Chromatography-Tandem Mass Spectrometry, Chuan Wang

Doctoral Dissertations

"Pharmaceutical and personal care products have benefited humans and animals around the world. However, their presence in natural and treated water system as emerging contaminates may have potentially adverse effects on the aquatic environment and cause development of bacterial resistance. In this research project, a comprehensive liquid chromatography tandem mass spectrometry method has been developed and validated for the analysis of sixteen pharmaceutical compounds using solid phase extraction. Treated and untreated water samples collected across Missouri from water treatment facilities were analyzed to access the distribution of sixteen pharmaceutical compounds in both winter and summer seasons. The results of the …

Enhanced Photorefractivity In A Polymeric Composite Photosensitized With Carbon Nanotubes Grafted To A Photoconductive Polymer, Naveen Kumar Lingam, Sonali Kalghatgi, Jeffrey G. Winiarz

Chemistry Faculty Research & Creative Works

We report on the photosensitization of photorefractive (PR) polymeric composites through the inclusion of multiwalled and singlewalled carbon nanotubes (CNTs), respectively, having poly(N -vinyl carbazole) (PVK) grafted to their surfaces. The PR nature of the holographic gratings was confirmed via the asymmetric exchange of energy in a two-beam-coupling (TBC) geometry, yielding TBC gain coefficients approaching 80 cm^-1. In addition, in degenerate-four-wave- mixing experiments the prepared composites exhibited diffraction efficiencies as high as 60% and overmodulation voltages as low as ∼40 V/μm. These notable figures of merit indicate that the grafting of the PVK polymer to the various CNTs …

Epitaxial Electrodeposition Of Metal Oxide Films And Superlattices Which Exhibit Resistance Switching, Rakesh V. Gudavarthy

Doctoral Dissertations

"This dissertation presents an investigation of the electrodeposition of metal oxide films and superlattices on conducting polycrystalline and single crystal substrates. In the first part of the study, electrodeposition of magnetite (Fe₃O₄) films and superlattices in the magnetite/zinc ferrite system which exhibit resistance switching is studied. Paper I reports the electrodeposition of superlattices in the magnetite/zinc ferrite system and shows that only superlattices exhibit multistate resistance switching. In paper II, simple polycrystalline magnetite films electrodeposited on stainless steel crystals exhibit multistate resistance switching which can be tuned by controlling the composition of the films. Paper II describes the epitaxial electrodeposition …

Relaxation Imaging To Characterize Lightweight Polymer-Crosslinked Aerogels, Emmalou T. Satterfield

Masters Theses

"Silica aerogels are three-dimensional assemblies of silica nanoparticles with extremely low densities. In some instances, the internal void volume is more than 90% of the total volume. The highly porous structure of the aerogels leads to attractive properties for thermal and noise insulation, due to very low thermal conductivity and very high acoustic impedance. The strength of silica aerogels has been substantially improved by casting a thin conformal polymer coating over the entire internal porous surfaces of the nanostructure. The coating reinforces the interparticle connections without significantly compromising the internal void space. To analyze and compare the properties of several …

Interfacial Effects On Dielectric Properties Of Polymer-Particle Nanocomposites, Sasidhar Siddabattuni

Doctoral Dissertations

"Dielectric materials that are capable of efficiently storing large amounts of electrical energy are desirable for many electronic and power devices. Since the electrical energy density in a dielectric material is limited to εV_b²/2, where ε is the dielectric permittivity of the material and V_b is the breakdown strength, increased permittivity and breakdown strength are required for large energy storage density. Interfacial effects can influence the dielectric properties, especially dielectric breakdown resistance in polymer-particle nanocomposites. Several functional organophosphates were used to modify the surface of titania and barium titanate nanofiller particles in order to achieve covalent interface …

Development Of A Versatile Man-Portable Obscurant Aerosol Generator: Characterization Of Aerosols In Laboratory And Field Environments, Robert William Schaub

Doctoral Dissertations

"The objective of research presented in this dissertation was to develop a readily deployable and environmentally benign obscurant system operating with a single liquid for the visible and near infrared regions. To achieve this objective, research efforts were directed in two areas: i. Evaluating suitable biogenic oils to replace the United States Army's "Fog Oil" as the obscurant fluid. ii. Design, fabrication and validation of a prototype man-portable / vehicle mountable modular obscurant aerosol generator. Petroleum middle distillate - "Fog Oil" has been the material of choice for wide area obscuration for several decades. Large quantities (thousands gallons) of the …

Part-I Characterization Of Phorbol Ester; The Predominant Toxic Component Of Jathropha Curcas And Development Of An Efficient Process For The Detoxification Of Jathropha Curcas Meal Part-Ii Quantification Of 2-Hydroxy-4-(Methylthio) Butanoic Acid And Pantothenic Acid In Bovine Serum And Sea Water Matrices, Balaji Viswanathan

Doctoral Dissertations

"Jatropha curcas is has often been touted as the most sustainable biofuel source. Jatropha curcas is a drought resistant perennial plant belonging to the Euphorbiaceae family. Interest in this plant as a biofuel source is related to high lipid (triglyceride) content of its seeds. However, economics of jatropha as a biofuel source has been marred by the toxicity of the oil and its protein rich meal. As a result of high toxicity the protein rich meal is used only as a very low or no economic value organic fertilizer. Economic return from jatropha can be dramatically enhanced through development of …

Synthesis And Binding Studies Of Peptide Mimetics, Anion Receptors, And Kinase Inhibitors, Nanditha G. Nair

Doctoral Dissertations

"A series of novel purine-based fluoroaryl triazoles were synthesized and assayed for their neuroprotective effects of hippocampal slice culture exposed to amyloid beta (Aß) oligomers. A monofluorinated triazole has been identified which has comparable neuroprotective effect as that of flavopiridol and roscovitine against the Aß induced neurotoxicity. Carnosine and histidine are biologically interesting antioxidants. In order to probe whether they exert their antioxidant effect through metal ion chelation, the Cu(ll) ion chelating abilities of these compounds were measured by UV-vis spectroscopy. Amyloid beta, the major component of senile plaques in Alzheimer's disease, is known to complex transition metal ions through …

Aerogels And Films Through Free Radical Polymerization, Anand G. Sadekar

Doctoral Dissertations

"Aerogels are porous lightweight materials, unique among all solids in terms of low density, low thermal conductivity, low dielectric constants and high acoustic attenuation. The penalty for those exceptional properties is fragility. That issue has been addressed by bridging covalently (crosslinking) the elementary nanoscopic building blocks of silica aerogels with polymers. To streamline the crosslinking process we synthesized a bidentate free radical initiator (Si-AIBN) that gets attached on the skeletal nanoparticles and induces crosslinking by surface initiated polymerization (SIP). Here, we extend the scope of Si-AIBN in two directions: (a) we demonstrate extremely adhering, covalently attached polymer coatings on oxidized …

One Pot Synthesis Of Metal, Carbides And Polymeric Aerogels, Naveen K. Chandrasekaran

Doctoral Dissertations

"Ultra-low density, three-dimensional assemblies of nanoparticles are referred to as aerogels, and typically are derived from supercritical fluid (SCF) drying of wet-gels. Aerogels are generally fragile materials, but that issue has been addressed successfully by X-aerogels, in which the inorganic nanoparticle framework plays the role of the template for the accumulation of polymer that connects covalently and crosslinks the nanoparticles. The resulting materials can be 300x stronger than the native network, for a nominal increase in density by a factor of 3x. Since the exceptional mechanical properties of X-aerogels are traced to the conformal polymer coating, it was reasonable to …

Preliminary Model Development Of Metal Complexation Of Polyester Derivatives Of 2,2'-Biimidazole, Shelonda Rena Taylor Finch

Doctoral Dissertations

"The objective of this study was to develop a chemical model for metal ion complex formation by a macroligand system with multi-metal binding sites using 2,2'-biimidazole as the starting molecule of the ligand system. Prior studies in this laboratory guided the selection of diesters and hydroxyethyl derivatives of 2,2'-biimidazole as model monomers. In addition, metal ion complexation studies with 2,2'-biimidazole derivatives were conducted. As a result, crystal structures of 1,1'-di(methylpropionato)-2,2-biimidazole, 2,2'-bis(1H-imidazolium) dinitrate and silver 2,2'-bis(1H-imidazolium) trinitrate, were reported. The crystal structures indicated a dependence upon the binding ability of the protonated 2,2'-biimidazole and counter ions. transesterification of the diesters and …

Nona-Arginine Facilitates Delivery Of Quantum Dots Into Cells Via Multiple Pathways, Yi Xu, Betty Revon Liu, Han Jung Lee, Katie Shannon, Jeffrey G. Winiarz, Tien-Chun Wang, Huey-Jenn Chiang, Yue-Wern Huang

Biological Sciences Faculty Research & Creative Works

Semiconductor quantum dots (QDs) have recently been used to deliver and monitor biomolecules, such as drugs and proteins. However, QDs alone have a low efficiency of transport across the plasma membrane. In order to increase the efficiency, we used synthetic nona-arginine (SR9), a cell-penetrating peptide, to facilitate uptake. We found that SR9 increased the cellular uptake of QDs in a noncovalent binding manner between QDs and SR9. Further, we investigated mechanisms of QD/SR9 cellular internalization. Low temperature and metabolic inhibitors markedly inhibited the uptake of QD/SR9, indicating that internalization is an energy-dependent process. Results from both the pathway inhibitors and …

Aspergillus Fumigatus Sida Is A Highly Specific Ornithine Hydroxylase With Bound Flavin Cofactor, Samuel W. Chocklett, Pablo Sobrado

Chemistry Faculty Research & Creative Works

Ferrichrome is a hydroxamate-containing siderophore produced by the pathogenic fungus Aspergillus fumigatus under iron-limiting conditions. This siderophore contains N5-hydroxylated l-ornithines essential for iron binding. A. fumigatus siderophore A (Af SidA) catalyzes the flavin- and NADPH-dependent hydroxylation of l-ornithine in ferrichrome biosynthesis. Af SidA was recombinantly expressed and purified as a soluble tetramer and is the first member of this class of flavin monooxygenases to be isolated with a bound flavin cofactor. The enzyme showed typical saturation kinetics with respect to l-ornithine while substrate inhibition was observed at high concentrations of NADPH and NADH. Increasing amounts of hydrogen peroxide were measured …

Influence Of Ambient Temperature On The Pm Emissions From A Gas Turbine Engine, Donald E. Hagen, Prem Lobo, Philip D. Whitefield, Max B. Trueblood

Physics Faculty Research & Creative Works

During Project AAFEX, PM emissions measurements were conducted on a CFM56-2C1 gas turbine engine in January 2009 in Palmdale CA. The engine was mounted on a NASA DC-8 aircraft, which was parked on the runway, and emission samples were extracted at the engine exit plane (1m), in the near field (30m), and in the advected plume (145m). The engine was operated at several power levels, and burned several fuels: JP-8, a Fischer-Tropsch fuel derived from natural gas (FT1), and a second Fischer-Tropsch fuel derived from gasified coal (FT2). In addition to these fuels, 50:50 blends of the Fischer-Tropsch fuels and …

Hydrogen Storage And Carbon Dioxide Capture In An Iron-Based Sodalite-Type Metal-Organic Framework (Fe-Btt) Discovered Via High-Throughput Methods, Kenji Sumida, Satoshi Horike, Steven S. Kaye, Zoey R. Herm, Wendy L. Queen, Craig M. Brown, Fernande Grandjean, Gary J. Long, Anne M. Dailly, Jeffrey R. Long

Chemistry Faculty Research & Creative Works

Using high-throughput instrumentation to screen conditions, the reaction between FeCl₂ and H₃BTT·2HCl (BTT^3- = 1,3,5-benzenetristetrazolate) in a mixture of DMF and DMSO was found to afford Fe₃[(Fe₄Cl)₃(BTT)₈] ₂·22DMF·32DMSO·11H₂O. This compound adopts a porous three-dimensional framework structure consisting of square [Fe₄Cl]⁷⁺ units linked via triangular BTT^3- bridging ligands to give an anionic 3,8-net. Mössbauer spectroscopy carried out on a DMF-solvated version of the material indicated the framework to contain high-spin Fe²⁺ with a distribution of local environments and confirmed the presence …

Effects Of Hydrogen Bonding On Vibrational Normal Modes Of Pyrimidine, Austin A. Howard, Gregory S. Tschumper, Nathan I. Hammer

Chemistry Faculty Research & Creative Works

The effects of weak intermolecular interactions on 10 vibrational normal modes of pyrimidine are investigated by Raman spectroscopy and electronic structure computations. Hydrogen-bonded networks of water induce a shift to higher energy in certain normal modes of pyrimidine with increasing water concentration, while other modes are relatively unaffected. Pyrimidine molecules also exhibit weak C-H⋯N interactions and shifted normal modes upon crystallization. The selective nature of the shifting of normal modes to higher energy allows for definitive assignments of the nearly degenerate ν8a and ν8b modes with polarized Raman spectroscopy. Natural bond orbital (NBO) analyses indicate that when water molecules donate …

Chemical Bath Deposition And Electrodeposition Of Epitaxial Semiconductor Materials For Application In Photovoltaic Devices, Guojun Mu

Doctoral Dissertations

"This dissertation investigates the chemical bath deposition of zinc oxide and electrodeposition of cuprous iodide on polycrystalline and single crystal substrates. Paper I describes the chemical bath deposition and characterization of titled epitaxial zinc oxide nanospears on Si(001) single crystal substrate. In Paper II, the chemical bath deposition of zinc oxide nanospears from highly alkaline solutions is discussed in detail, including a thermodynamic calculation of saturation and speciation of Zn(II) in aqueous solution, and a kinetic study of the deposition process. In this paper the epitaxial zinc oxide is reported grown on Au(100), (110), and (111) single crystals. Paper III …

Capillary Electrophoresis Of Pteridines In Urine And Plants And Quantification Of Pharmaceutical And Personal Care Products In Missouri Waste Water, Stephen E. Gibbons

Doctoral Dissertations

"Capillary electrophoresis (CE) is a powerful technique that separates molecules based on their respective charge and hydrodynamic size. The major advantages of CE are high separation efficiency, small sample volume requirements, simple to no sample preparation and often organic solvents are not required for the separation.

The work presented in this dissertation utilized capillary electrophoresis for the analysis two different classes of compounds in different matrices. The first project investigated pteridines in urine and plants. The second project investigated pharmaceutical and personal care products (PPCP's) in Missouri waste water.

As cancer continues to be one of the top three causes …

Water Analysis For Emerging Environmental Contaminants, Xiaoliang Cheng

Masters Theses

"The presence of emerging environmental contaminants in water bodies used either as drinking water or for recreational purpose has received considerable attention in the recent years. The emerging environmental contaminants can be defined as a wide range of chemicals that have been determined in the environment which may present serious health risks for humans. The occurrence of these contaminants indicate that both household and industrial chemicals have been introduced to water resources, a wide variety of chemicals, such as disinfection byproducts, pharmaceutical and personal care products and so on, have been detected at cetiain levels in either water bodies or …

Comparing The Chelating Abilities Of N-Acetylcysteine And N-Acetylcysteine Amide In Vitro For Lead Poisoning Treatment, Weiqing Chen

Masters Theses

"Lead poisoning is a perennial and serious health problem around the world. The daily widespread use of lead has dramatically increased the degree and longevity of its exposure to humans, exacerbating the task of lead poisoning treatment. Lead exerts adverse effects on cardiovascular, central nervous, renal, gastrointestinal, and reproductive systems. The common treatment for lead poisoning is chelation therapy. Chelators were proposed to treat lead poisoning a very long time ago. However, chelators have severe side effects that could cause more problems, in addition to lead poisoning. Therefore, another group of drugs has been suggested --- antioxidants. This type of …

Analysis And Occurrence Of Disinfection By-Products In Fresh And Salt Water, Honglan Shi

Doctoral Dissertations

"Haloacetic acids, trihalomethanes, and bromate are important toxic water disinfection by-products (DBPs) that the US Environmental Protection Agency (USEPA) regulates in drinking water. Iodoacetic acids and halonitromethanes (HNMs) are the unregulated emerging DBPs that have been recently found in the disinfected drinking waters, and which have much higher toxicity than the regulated DBPs. The purpose of this study was to develop new analytical methods for analysis of these emerging DBPs, to study their occurrence in Missouri drinking water systems, and to investigate the occurrence and formation of these DBPs in saltwater and seawater based marine park aquaria. A new rapid …

Haart Drugs Induce Oxidative Stress And Mitochondrial Dysfunction In Blood-Brain Barrier, Kalyan Reddy Manda

Doctoral Dissertations

"The era of highly active antiretroviral therapy (HAART) has controlled AIDS and its related disorders considerably; however, the prevalence of HIV-1-associated neurocognitive disorders (HAND) has been on the rise in the post-HAART era. In view of these developments, we investigated whether a HAART drug combination of 3'-Azido-2', 3'-deoxythymidine (AZT) and Indinavir (IDV) can alter the functionality of the blood-brain barrier (BBB) endothelial cells, thereby exacerbating the condition. Viability of hCMEC/D3 cells (in vitro model of BBB) that were exposed to the drugs was significantly reduced after a 72 hr treatment, in a dose-dependent manner. Reactive oxygen species (ROS) were highly …

The Stereochemistry Of Selected Supramolecular Complexes Of Cucurbiturils And The Effect Of Homogeneous Equilibria And Electron Transfer Of The Guest, Arumugam Thangavel

Doctoral Dissertations

"From a practical perspective, host-guest complexes are vehicles for understanding and using supramolecular interactions for purposeful function in sensors, molecular machines and switches, while from a fundamental perspective they may lead to novel supramolecular protection schemes in basic organic reactions. This dissertation examines the interactions of cucurbiturils as barrel-shaped hosts, exhibiting a hydrophobic cavity, with substituted benzoylpyrydinium, phenypyrylium, and diazaanthraquinonediium cations as guests. In water, N-methyl-4-(p-substituted benzoyl)pyridinium cations exist in equilibrium with their hydrated forms (gem-diols), whose concentrations depend on the para substituent. In the presence of cucurbit7uril (CB[7]), the benzoyl group shows a preference for the CB[7] cavity, and …

Adsorption And Segmental Dynamics Of Acrylate And Methacrylate Polymers Adsorbed On A Silica Surface, Piyawan Krisanangkura

Doctoral Dissertations

"Poly(isopropyl acrylate)-d₇ (PIPA- d₇) was studied using ²H solid-state NMR and modulated differential scanning calorimetry (MDSC). The polymer was deuterated on the methyl groups and side-chain methine. The PIPA- d₇ was adsorbed onto Cab-O-Sil silica. These two types of deuterons each showed their own characteristic deuterium nuclear magnetic resonance (NMR) spectra for bulk PIPA- d₇. The ²H NMR spectra of adsorbed PIPA- d₇ samples showed the presence of heterogeneity of the segmental dynamics. A residual powder pattern was found in the spectra of the surface samples at higher temperatures, indicating that the segments were tightly attached to the silica. The …

Nmr Investigations Of Biomass-To-Fuel Conversions By Hydrothermal Processes, Wenjia Zhang

Doctoral Dissertations

"Biofuels have gained significant attention as the most promising alternative energy and fuel supply for the near future because of two dominant reasons: first, biofuels are environmentally friendly; and second, they afford a sustainable technology. Biofuels can be synthesized from biomass by several different processes, among which, hydrothermal conversion is considered to be more energy efficient. However, scientific efforts to improve hydrothermal biomass-to-fuel (HT-BTF) conversion efficiencies are severely limited because little is known about the salient reaction mechanisms and intermediates. This study is aimed at a better understanding of the hydrothermal biomass degradation kinetics by advanced NMR spectroscopy and, accordingly, …

Effect Of Structure And Plasticizer On The Glass Transition Of Adsorbed Polymer, Boonta Hetayothin

Doctoral Dissertations

"The effect of molecular mass on adsorbed poly(methyl methacrylate) (PMMA) on silica was determined using temperature-modulated differential scanning calorimetry (TMDSC). A two-component model, based on loosely-bound polymer (glass transition temperature, T_g, similar to that of bulk) and tightly-bound polymer (T_g higher than that of bulk) was used to interpret the thermograms. Similar amounts of tightly-bound polymer were found for 450 and 85 kDa PMMA (0.78 mg/m²), while the 32 kDa sample had a smaller amount (0.48mg/m²). A comparison of adsorbed PMMA, poly(vinyl acetate) (PVAc), and poly(methyl acrylate) (PMA) on silica was made using the same technique. The …

Analysis Of Globule Types In Malignant Melanoma, Jin Xu, Kapil Kumar Gupta, William V. Stoecker, Yamini Krishnamurthy, Harold S. Rabinovitz, Austin Bangert, David A. Calcara, Margaret C. Oliviero, Joseph M. Malters, Rhett J. Drugge, R. Joe Stanley, Randy Hays Moss, Mehmed Emre Celebi

Chemistry Faculty Research & Creative Works

Objective: To identify and analyze subtypes of globules based on size, shape, network connectedness, pigmentation, and distribution to determine which globule types and globule distributions are most frequently associated with a diagnosis of malignant melanoma. Design: Retrospective case series of dermoscopy images with globules. Setting: Private dermatology practices. Participants: Patients in dermatology practices. Intervention: Observation only. Main Outcome Measure: Association of globule types with malignant melanoma. Results: The presence of large globules (odds ratio [OR], 5.25) and globules varying in size (4.72) or shape (5.37) had the highest ORs for malignant melanoma among all globule types and combinations studied. Classical …