Physical Sciences and Mathematics Commons^™

An Investigation Into A Microwave-Enhanced Solvent-Free Mannich Condensation Reaction, Kristy Lynn Homburger

Masters Theses

Microwave irradiation has gained in popularity in recent years since it has been found to accelerate various chemical reactions. Microwaves are generally considered to be more environmentally friendly than traditional methods for activating chemical reactions. An investigation into a microwave-enhanced, solventless Mannich condensation was performed. The efficiency of a standard household microwave was compared to that of an industrial microwave, with the industrial microwave proving to be more effective. The advantages of using microwave irradiation for a Mannich condensation include milder reaction conditions, the absence of solvent, less waste, and shorter reaction times. The reaction between terminal alkynes, secondary amines, …

Free Radical Polymerization In Room Temperature Ionic Liquids, Xiao Ma

Masters Theses

No abstract provided.

Structural And Dynamical Studies Of Superacids And Superacidic Solutions Using Neutron And High Energy X-Ray Scattering, Jamie John Molaison

Masters Theses

The diffusive motions of the Brønsted superacid, hydrogen fluoride, have been studied using quasielastic neutron scattering. Neutron and high energy X-ray diffraction measurements on the Lewis superacid, antimony pentafluoride, are presented along with the results of three applied data models. Finally, structural information was obtained for a 9:1 FSO₃H:NH₃ solution using neutron diffraction with isotopic substitution and nuclear magnetic resonance.

Characterization Of Polar Organic Components In Fine Aerosols In The Southeastern United States: Identity, Origin, And Evolution, Song Gao, Jason D. Surratt, Eladio M. Knipping, Eric S. Edgerton, Mona Shahgholi, John H. Seinfeld

Chemistry and Physics Faculty Articles

Filter samples of fine aerosols collected in the Southeastern United States in June 2004 were analyzed for the characterization of polar organic components. Four analytical techniques, liquid chromatography –mass spectrometry, ion trap mass spectrometry, laser desorption ionization mass spectrometry, and high-resolution mass spectrometry, were used for identification and quantification. Forty distinct species were detected, comprising on average 7.2% and 1.1% of the total particulate organic mass at three inland sites and a coastal site, respectively. The relative abundance of these species displays a rather consistent distribution pattern in the inland region, whereas a different pattern is found at the coastal …

Photoreductive Dissolution Of Ferrihydrite By Methanesulfinic Acid: Evidence Of A Direct Link Between Dimethylsulfide And Iron-Bioavailability, Anne M. Johansen, Jennifer M. Key

All Faculty Scholarship for the College of the Sciences

Within open‐ocean regions where excess macronutrients are present, phytoplankton growth is limited by the bioavailability of iron supplied to these areas primarily within atmospheric aerosols of crustal origin. However, processes that control the abundance of biologically accessible iron in these aerosols are largely unknown. Here we show that dissolution of ferrihydrite, a surrogate iron(oxy)hydroxide phase found in atmospheric waters, is enhanced in the presence of methanesulfinic acid (MSIA, CH₃SO₂H, a dimethylsulfide (DMS) oxidation intermediate) in laboratory irradiation experiments with aqueous suspensions that simulate marine aerosol particles. The increased release of soluble Fe(II) is attributed to a …

Structure-Activity Studies Of Glycosphingolipids As Antigens Of Natural Killer T Cells, Randal Donald Goff

Theses and Dissertations

Glycosphingolipids (GSLs), composed of a polar saccharide head and a lipophilic ceramide tail, are ubiquitous components of the plasma membrane of eukaryotic cells. They serve in many regulatory capacities and have antigenic properties towards natural killer T (NKT) cells of the innate immune system. Critical to the recognition of glycosylceramides by NKT cells are antigen presenting cells (APC), such as dendritic cells, which are responsible for binding, processing, and delivery of ligands to these lymphocytes. This event is mediated by CD1d, a major histocompatibility complex-like protein expressed on the surface of APCs, which binds GSL antigens by the ceramide moiety …

Polyethylene And Polypropylene Nanocomposites Based On Polymerically - Modified Clay Containing Alkylstyrene Units, Jinguo Zhang, Charles A. Wilkie

Chemistry Faculty Research and Publications

Sodium montmorillonite was modified with a new polymeric surfactant. The high molecular weight of the surfactant appears to have led to incomplete cation exchange of the clays, but did promote nanocomposite formation with polyethylene and polypropylene. X-ray diffraction combined with transmission electron microscopy revealed a mixed nanocomposite morphology. The thermal stability of the nanocomposites was evaluated by thermogravimetric analysis, while flammability of the nanocomposites was evaluated by cone calorimetry. A significant 40% reduction in peak heat release rate was observed at 10% organo-clay (3% inorganic clay) loading with an even higher 50% reduction at a loading level of 16% modified …

48th Rocky Mountain Conference On Analytical Chemistry

Rocky Mountain Conference on Magnetic Resonance

Final program, abstracts, and information about the 48th annual meeting of the Rocky Mountain Conference on Analytical Chemistry, co-endorsed by the Colorado Section of the American Chemical Society and the Rocky Mountain Section of the Society for Applied Spectroscopy. Held in Breckenridge, Colorado, July 23-27, 2006.

Comparison Of Protein Active Site Structures For Functional Annotation Of Proteins And Drug Design, Robert Powers, Jennifer C. Copeland, Katherine Germer, Kelly A. Mercier, Viswanathan Ramanathan, Peter Revesz

Robert Powers Publications

Rapid and accurate functional assignment of novel proteins is increasing in importance, given the completion of numerous genome sequencing projects and the vastly expanding list of unannotated proteins. Traditionally, global primary-sequence and structure comparisons have been used to determine putative function. These approaches, however, do not emphasize similarities in active site configurations that are fundamental to a protein’s activity and highly conserved relative to the global and more variable structural features. The Comparison of Protein Active Site Structures (CPASS) database and software enable the comparison of experimentally identified ligand-binding sites to infer biological function and aid in drug discovery. The …

Accumulation Of Phycotoxins In The Mussel Mytilus Galloprovincialis From The Central Adriatic Sea, Maja Pavela-Vrančić, Ivana Ujević, Živana Ninčević Gladan, Ambrose Furey

Physical Sciences Publications

Surveys of DSP (Diarrheic Shellfish Poisoning) toxin profiles in the mussel Mytilus galloprovincialis from coastal waters of the central Adriatic Sea, over the years 1995 to 2001, demonstrate that incidents of shellfish toxicity in this area are dominated by the occurrence of okadaic acid (OA) and a PTX derivative, 7-epi-pectenotoxin-2-seco acid (7-epi-PTX-2SA). Toxin composition and the relative ratio of toxic components in shellfish is in correlation with the occurrence of DSP producing organisms from the Dinophysis species along with Prorocentrum micans and Lingulodinium polyedrum. The occurrence of D. sacculus shortly before the appearance of OA in shellfish implicates its possible …

The Effect Of Protein Dielectric Coefficient On The Ionic Selectivity Of A Calcium Channel, Douglas Henderson, Dezso Boda, Monika Valisko, Bob Eisenberg, Wolfgang Nonner, Dirk Gillespie

Faculty Publications

Calcium-selective ion channels are known to have carboxylate-rich selectivity filters, a common motif that is primarily responsible for their high Ca2+ affinity. Different Ca2+ affinities ranging from micromolar (the L-type Ca channel) to millimolar (the ryanodine receptor channel) are closely related to the different physiological functions of these channels. To understand the physical mechanism for this range of affinities given similar amino acids in their selectivity filters, we use grand canonical Monte Carlo simulations to assess the binding of monovalent and divalent ions in the selectivity filter of a model Ca channel. We use a reduced model where the electrolyte …

Shape-Persistent Macrocyclic Aromatic Tetrasulfonamides: Molecules With Nanosized Cavities And Their Nanotubular Assemblies In Solid State, Lan He, Yu An, Lihua Yuan, Wen Feng, Minfeng Li, Dechun Zhang, Kazuhiro Yamato, Chong Zheng, Xiao Cheng Zeng, Bing Gong

Xiao Cheng Zeng Publications

Alkoxy side-chain-flanked diarylsulfonamide serves as a reliable structural motif for constructing macrocyclic aromatic tetrasulfonamides. This 90° structural motif is persistent both in solution and in the solid state, which allows the one-step formation of tetrasulfonamide macrocycles. These macrocycles adopt a cone-shaped conformation in solution and in the solid state. For each molecule, an interior cavity surrounded by the aromatic residues is formed. The cavity sizes of the macrocycles can be tuned by incorporating aromatic residues of proper sizes. Guest (solvent) molecules are found in the cavities and bound by side chains. In solution, ¹H NMR shows that the cone …

Syntheses Of Aza Analogs Of Kainoids, Mingping Di

FIU Electronic Theses and Dissertations

The kainoids are a class of non-proteinogenic pyrrolidine dicarboxylates that exhibit both excitatory and excitotoxic activities. These activities are a result of the ability of the kainoids to act as glutamate receptor agonists by activating ionotropic glutamate receptors. The parent of this group of compounds is x-kainic acid. Kainic acid is isolated from the seaweed Diginea simplex and has been used in Asian countries as a treatment for intestinal worms in children. In addition it is used extensively by neuropharmacologists for the study of glutamate receptors. Several years ago, the world's sole supplier of kainic acid discontinued this product. Since …

10,10′-Dinitro-10,10′-(Butane-1,4-Di­Yl)Dianthracen-9(10h)-One, Mustafa Arslan, Erol Asker, John Masnovi, Ronald J. Baker

Chemistry Faculty Publications

The title compound, C₃₂H₂₄N₂O₆, was obtained as the decomposition product of (E,E)-1,4-bis­[9,10-dihydro-9-nitro-10-(trinitro­meth­yl)-9-anthr­yl]butane, which was synthesized via a photochemical reaction of 1,4-bis­(9-anthr­yl)butane with tetra­nitro­methane. The asymmetric unit contains one half-mol­ecule; the complete mol­ecule is generated by a center of inversion. The crystal packing is determined mainly by inter­molecular C—H⋯O inter­actions.

Novel Potentiometric And Optical Silver Ion-Selective Sensors With Subnanomolar Detection Limits, Zsófia Szigeti, Adam Malon, Tamás Vigassy, Viktor Csokai, Alajos Grün, Katarzyna Wygladacz, Nan Ye, Chao Xu, Vincent J. Chebny, István Bitter, Rajendra Rathore, Eric Bakker, Ernö Pretsch

Chemistry Faculty Research and Publications

Ten Ag⁺-selective ionophores have been characterized in terms of their potentiometric selectivities and complex formation constants in solvent polymeric membranes. The compounds with π-coordination show much weaker interactions than those with thioether or thiocarbamate groups as the coordinating sites. Long-term studies with the best ionophores show that the lower detection limit of the best Ag⁺ sensors can be maintained in the subnanomolar range for at least 1 month. The best ionophores have also been characterized in fluorescent microspheres. The so far best lower detection limits of 3 × 10⁻¹¹ M (potentiometrically) and 2 × 10^{−11 …}

Natural Organic Matter And Colloid-Facilitated Arsenic Transport And Transformation In Porous Soil Media, Zhangrong Chen

FIU Electronic Theses and Dissertations

Prediction of arsenic transport and transformation in soil environment requires understanding the transport mechanisms and proper estimation of arsenic partitioning among all three phases in soil/aquifer systems: mobile colloids, mobile soil solution, and immobile soil solids. The primary purpose of this research is to study natural dissolved organic matter (DOM)/colloid-facilitated transport of arsenic and understand the role of soil derived carriers in the transport and transformation of both inorganic and organoarsenicals in soils.

DOM/colloid facilitated arsenic transport and transformation in porous soil media were investigated using a set of experimental approaches including batch experiment, equilibrium membrane dialysis experiment and column …

The Runge-Lenz Vector, Carl W. David

Chemistry Education Materials

The Runge-Lenz vector is a constant of the motion in the Kepler problem. As a precursor to developing a ladder operator formalism for the H-atom's quantum mechanics, various relations concerning the Runge-Lenz vector are obtained.

Dna-Templated Surface Alignment And Characterization Of Carbon Nanotubes., Huijun Xin

Theses and Dissertations

Carbon nanotubes are appealing materials for nanofabrication due to their unique properties and structures. However, for carbon nanotubes to be used in mass-fabricated devices, precise control of nanotube orientation and location on surfaces is critical. I have developed a technique to align single-walled carbon nanotubes (SWNTs) on surfaces from a droplet of nanotube suspension under gas flow. Fluid motion studies indicate that alignment is likely due to circulation of SWNTs in the droplet. My work provides a facile method for generating oriented nanotubes for nanodevice applications. I have also devised an approach for localizing SWNTs onto 1-pyrenemethylamine-decorated DNA on surfaces. …

The Structural Integrity Of Anion Binding Exosite I Of Thrombin Is Required And Sufficient For Timely Cleavage And Activation Of Factor V And Factor Viii, Michael A. Bukys, Tivadar Orban, Paul Y. Kim, Daniel O. Beck, Michael E. Nesheim, Michael Kalafatis

Chemistry Faculty Publications

Alpha-thrombin has two separate electropositive binding exosites (anion binding exosite I, ABE-I and anion binding exosite II, ABE-II) that are involved in substrate tethering necessary for efficient catalysis. Alpha-thrombin catalyzes the activation of factor V and factor VIII following discrete proteolytic cleavages. Requirement for both anion binding exosites of the enzyme has been suggested for the activation of both procofactors by alpha-thrombin. We have used plasma-derived alpha-thrombin, beta-thrombin (a thrombin molecule that has only ABE-II available), and a recombinant prothrombin molecule rMZ-II (R155A/R284A/R271A) that can only be cleaved at Arg(320) (resulting in an enzymatically active molecule that has only ABE-I …

Enhanced Electrospray Ionization For Mass Spectrometry And Ion Mobility Spectrometry, Li Zhou

Theses and Dissertations

Electrospray ionization (ESI) has become one of the most commonly used ionization techniques for mass spectrometry (MS) and ion mobility spectrometry (IMS), and efforts continue to improve its performance. ESI-MS is most recognized for its wide application to biomacromolecules where high sensitivity is of paramount importance. However, the major limitation in sensitivity with ESI-MS is due to its low ion transmission efficiency from the ESI source into the sampling orifice and through any stages utilized for transfer of ions from atmosphere to vacuum in the MS. A series of atmospheric pressure ion focusing interfaces were designed and implemented to enhance …

Electric Field Gradient Focusing-Uv Detection For Protein Analysis, Shu-Ling Lin

Theses and Dissertations

Electric field gradient focusing (EFGF) utilizes a hydrodynamic flow and an electric field gradient to focus and concentrate charged analytes and order them in a separation channel according to electrophoretic mobility. Elution can be achieved by decreasing the applied voltage or increasing the hydrodynamic flow. EFGF has the advantages of concentrating a large volume (100 micro-L) of target proteins without significant band broadening and simultaneously removing unwanted components from the sample. Two types of EFGF devices have been investigated to concentrate and separate proteins: a fiber-based EFGF device and a hydrogel-based EFGF device. Using fiber-based EFGF with UV detection, a …

Structure And Enhanced Reactivity Rates Of The D 5 H Sc3n@ C80 And Lu3n@ C80 Metallofullerene Isomers: The Importance Of The Pyracylene Motif, Ting Cai, Liaosa Xu, Mark Anderson, Zhongxin Ge, Tianming Zuo, Xuelei Wang, Marilyn Olmstead, Alan Balch, Harry Gibson, Harry Dorn

Mark R. Anderson

In this paper we report enhanced reactivity of the D5h isomers in comparison with the more common Ih isomers of Sc3N@C80 and Lu3N@C80 toward Diels−Alder and 1,3-dipolar tritylazomethine ylide cycloaddition reactions. Also, the structure of the D5h isomer of Sc3N@C80 has been determined through single-crystal X-ray diffraction on D5h-Sc3N@C80·Ni(OEP)·2benzene (OEP = octaethylporphyrin). The Sc3N portion of D5h-Sc3N@C80 is strictly planar, but the plane of these four atoms is tipped out of the noncrystallographic, horizontal mirror plane of the fullerene by 30°. The combination of short bond length and high degree of pyramidization for the central carbon atoms of the pyracylene …

Structural And Electronic Properties Of Gd@C60: All-Electron Relativistic Total-Energy Study, Jing Lu, Wai-Ning Mei, Yi Gao, Xiao Cheng Zeng, Mingwei Jing, Guangping Li, Renat F. Sabirianov, Zhengxiang Gao, Liping You, Jun Xu, Dapeng Yu, Hengqiang Ye

Xiao Cheng Zeng Publications

Water soluble Gd-based metallofullerenes have potential application as magnetic resonance imaging contrast agent due to its higher proton relaxivities and lower toxicity. In this letter, we have investigated the structural and electronic properties of Gd@ C₆₀, which is the most abundantly produced Gd-based metallofullerene in carbon arc process, by using all-electron relativistic density functional theory. It is found that the Gd³⁺ ion is bonded to a hexagonal ring of C₆₀ by electrostatic interaction. The total spin multiplicity of Gd@C₆₀ is S = 7. The Gd atomic orbitals are hybridized with the C₆₀ molecular orbitals.

Crown Ether-Metal ‘Sandwiches’ As Linking Mechanisms In Assembled Nanoparticle Films, Rebecca R. Pompano, Phillip G. Wortley, Leslie M. Moatz, D. J. Tognarelli, Kevin W. Kittredge, Michael C. Leopold

Chemistry Faculty Publications

Crown ether ligands attached to monolayer-protected clusters (MPCs) were assembled as films and the linking mechanism between the crown ether–metal ion–crown ether bridges between nanoparticles was examined. Thicker films exhibited a red shift in the absorbance maximum for the surface plasmon band which was attributed to the increasing aggregation and cross linking within the film. Quantized double layer charging peaks suggest that film growth is selective toward a specific core size or exchange rate, either of which affect the number of potential linking ligands in the periphery of the MPCs. Multi-layer growth of films was only achieved with metal ions …

Adsorption Of Transition-Metal Atoms On Boron Nitride Nanotube: A Density-Functional Study, Xiaojun Wu, Xiao Cheng Zeng

Xiao Cheng Zeng Publications

Adsorption of transition atoms on a (8,0) zigzag single-walled boron nitride (BN) nanotube has been investigated using density-functional theory methods. Main focuses have been placed on configurations corresponding to the located minima of the adsorbates, the corresponding binding energies, and the modified electronic properties of the BN nanotubes due to the adsorbates.We have systemically studied a series of metal adsorbates including all 3d transition-metal elements (Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn) and two group-VIIIA transition-metal elements (Pd and Pt). We found that many transition-metal atoms can be chemically adsorbed on the outer surface of the …

Staphylococcus Aureus Helicase But Not Escherichia Coli Helicase Stimulates S. Aureus Primase Activity And Maintains Initiation Specificity, Scott A. Koepsell, Marilynn A. Larson, Mark A. Griep, Steven H. Hinrichs

Mark Griep Publications

Bacterial primases are essential for DNA replication due to their role in polymerizing the formation of short RNA primers repeatedly on the lagging-strand template and at least once on the leading-strand template. The ability of recombinant Staphylococcus aureus DnaG primase to utilize different single-stranded DNA templates was tested using oligonucleotides of the sequence 5’-CAGA (CA) ₅ XYZ (CA) ₃-3’, where XYZ represented the variable trinucleotide. These experiments demonstrated that S. aureus primase synthesized RNA primers predominately on templates containing 5’-d(CTA)-3’ or TTA and to a much lesser degree on GTA-containing templates, in contrast to results seen with the Escherichia …

High-Voltage Parallel Writing On Iron Nitride Thin Films, N. Farkas, J. D. Ehrman, Edward A. Evans, R. D. Ramsier, J. A. Dagata

Chemical, Biomolecular, and Corrosion Engineering Faculty Research

We report large area patterning of sputter-deposited FeN thin films by a high-voltage parallel writing technique that was recently developed to modify ZrN surfaces. Systematically patterned 15-100-nm-thick FeN films consisting of features with well-defined sizes and shapes are obtained by applying high dc voltages between a stamp and the samples. During the process the oxide dissolves, exposing the substrate beneath. This controlled breakdown eliminates the need for any postexposure etching. The single-step imprinting method presented here provides an emerging route to fabricate isolated FeN geometrical structures on silicon substrates for magnetic applications. (c) 2006 American Vacuum Society.

Formation Of Monofunctional Cisplatin-Dna Adducts In Carbonate Buffer, Alexandra Binter, Jerry Goodisman, James C. Dabrowiak

Chemistry - All Scholarship

Carbonate in its various forms is an important component in blood and the cytosol. Since, under conditions that simulate therapy, carbonate reacts with cisplatin to form carbonato complexes, one of which is taken up and/or modified by the cell [C.R. Centerwall, J. Goodisman, D.J. Kerwood, J. Am. Chem. Soc., 127 (2005) 12768–12769], cisplatin-carbonato complexes may be important in the mechanism of action of cisplatin. In this report we study the binding of cisplatin to pBR322 DNA in two different buffers, using gel electrophoresis. In 23.8 mM HEPES, N-(2-hydroxyethyl)-piperazine-N′-2-ethanesulfonic acid, 5 mM NaCl, pH 7.4 buffer, cisplatin produces …

Adsorption Of Hydrogen Molecules On The Platinum-Doped Boron Nitride Nanotubes, Xiaojun Wu, J.L. Yang, Xiao Cheng Zeng

Xiao Cheng Zeng Publications

Adsorption of hydrogen molecules on platinum-doped single-walled zigzag (8,0) boron nitride (BN) nanotube is investigated using the density-functional theory. The Pt atom tends to occupy the axial bridge site of the BN tube with the highest binding energy of −0.91 eV. Upon Pt doping, several occupied and unoccupied impurity states are induced, which reduces the band gap of the pristine BN nanotube. Upon hydrogen adsorption on Pt-doped BN nanotube, the first hydrogen molecule can be chemically adsorbed on the Pt-doped BN nanotube without crossing any energy barrier, whereas the second hydrogen molecule has to overcome a small energy barrier of …

Three-Terminal Devices To Examine Single Molecule Conductance Switching, Z K. Keane, Jacob W. Ciszek, J M. Tour, D Natelson

Chemistry: Faculty Publications and Other Works

We report electronic transport measurements of single-molecule transistor devices incorporating bipyridyl-dinitro oligophenylene-ethynylene dithiol (BPDN-DT), a molecule known to exhibit conductance switching in other measurement configurations. We observe hysteretic conductance switching in 8% of devices with measurable currents, and find that dependence of the switching properties on gate voltage is rare when compared to other single-molecule transistor devices. This suggests that polaron formation is unlikely to be responsible for switching in these devices. We discuss this and alternative switching mechanisms.