Physical Sciences and Mathematics Commons^™

Aerosol Properties And Chemical Apportionment Of Aerosol Optical Depth At Locations Off The U.S. East Coast In July And August 2001, Brian I. Magi, Peter V. Hobbs, Thomas W. Kirchstetter, Tihomir Novakov, Dean A. Hegg, Song Gao, Jens Redemann, Beat Schmid

Chemistry and Physics Faculty Articles

Airborne in situ measurements of vertical profiles of the aerosol light scattering coefficient, light absorption coefficient, and single scattering albedo (ω₀) are presented for locations off the East Coast of the United States in July–August 2001. The profiles were obtained in relatively clean air, dominated by airflows that had passed over Canada and the Atlantic Ocean. Comparisons of aerosol optical depths (AODs) at 550 nm derived from airborne in situ and sun-photometer measurements agree, on average, to within 0.034 ± 0.021. A frequency distribution of ω₀ measured in the atmospheric boundary layer off the coast yields …

Synthesis And Characterization Of Mercury Vapor Coordination Species Using 1,3-Benzenedioethanethiolate (Bdet), Elizabeth Zuchek, Harvest L. Collier

Opportunities for Undergraduate Research Experience Program (OURE)

Mercury is a major pollutant in the air today. Some possible chelators that have been used are British anti-Lewisite (BAL) 2,3-dimercaptopropanol, dimercaptosuccinic acid (DMSA). diinercaptopropanesulfonic acid (DMPS). and 1,3-benzenediamidoethanethiolate (BDE'I1. All contain two thiol groups, which 'capture' the heavy mercury element. Due to their structure, they all differ in how well they bind to the mercury atom. BDET is the most recent and efficient chelate used. Statistics show that coal-fired power plants are the nation's largest mercury polluter. Steps have been taken to lower the emission of this toxic metal by the Clean Air Act. However, recently The Bush Administration's …

26Al-Containing Acidic And Basic Sodium Aluminum Phosphate Preparation And Use In Studies Of Oral Aluminum Bioavailability From Foods Utilizing 26Al As An Aluminum Tracer, Robert A. Yokel, Aaron A. Urbas, Robert A. Lodder, John P. Selegue, Rebecca L. Florence

Pharmaceutical Sciences Faculty Publications

We synthesized ²⁶Al-containing acidic and basic (alkaline) sodium aluminum phosphates (SALPs) which are FDA-approved leavening and emulsifying agents, respectively, and used them to determine the oral bioavailability of aluminum incorporated in selected foods. We selected applicable methods from published syntheses (patents) and scaled them down (∼3000- and 850-fold) to prepare ∼300–400 mg of each SALP. The ²⁶Al was incorporated at the beginning of the syntheses to maximize ²⁶Al and ²⁷Al equilibration and incorporate the ²⁶Al in the naturally-occurring Al-containing chemical species of the products. Near infrared spectroscopy (NIR) and X-ray powder diffraction (XRD) were used …

Synthetic And Structural Studies Of Novel 1, 10-Phenanthroline Derivatives, Eunjoo Kim

Masters Theses

Asymmetric catalysis can provide a general approach to the preparation of enantiomerically enriched compounds in organic synthesis. Very often these asymmetric catalysts consist of a chiral ligand-metal complex. Because of the growing demand to develop enantioselective reactions in organic chemistry one focus of this area of research is the design and characterization of new chiral ligands for asymmetric synthesis.

The focus of my research is in the design, synthesis, and characterization of novel 1, 10-phenanthroline derivatives that could be used as chiral ligands in enantioselective reactions. Central to these studies have been the effect of substituents on the B-ring of …

Methods For Fabricating Microarrays Of Motile Bacteria, Sergey Rozhok, Clifton K. -F. Shen, Pey-Lih H. Littler, Zhifang Fan, Chang Liu, Chad A. Mirkin, Richard C. Holz

Chemistry Faculty Research and Publications

Motile bacterial cell microarrays were fabricated by attaching Escherichia coli K-12 cells onto predesigned 16-mercaptohexadecanoic acid patterned microarrays, which were covalently functionalized with E. coli antibodies or poly-L-lysine. By utilizing 11-mercaptoundecyl-penta(ethylene glycol) or 11-mercapto-1-undecanol as passivating molecules, nonspecific binding of E. coli was significantly reduced. Microcontact printing and dip-pen nanolithography were used to prepare microarrays for bacterial adhesion, which was studied by optical fluorescence and atomic force microscopy. These data indicate that single motile E. coli can be attached to predesigned line or dot features and binding can occur via the cell body or the flagella of bacteria. Adherent bacteria …

Double-Stranded Rna-Dependent Protein Kinase (Pkr) Is Downregulated By Phorbol Ester, Yan Zhou, Barbara I. Chase, Mark Whitmore, Bryan R.G. Williams, Aimin Zhou

Chemistry Faculty Publications

The double-stranded RNA-dependent protein kinase (PKR) is one of the key mediators of interferon (IFN) action against certain viruses. PKR also plays an important role in signal transduction and immunomodulation. Understanding the regulation of PKR activity is important for the use of PKR as a tool to discover and develop novel therapeutics for viral infections, cancer and immune dysfunction. We found that phorbol 12-myristate 13-acetate (PMA), a potent activator of protein kinase C (PKC), decreased the level of autophosphorylated PKR in a dose- and time-dependent manner in IFN-treated mouse fibroblast cells. Polyinosinic–polycytidylic acid (poly I:C) treatment enhanced the activity of …

Copper Exchange Studies Between The First And Fourth N-Terminal Metal-Binding Domains Of Wilson Disease Atpase, Jennifer Bunce

Masters Theses

The human copper-transporting ATPase Wilson's disease protein was one of the first proteins shown to be actively involved in cellular copper homeostasis. The protein includes six N-terminal metal binding domains. The individual capabilities of the domains to bind and transfer copper are not yet fully understood. Each metal-binding domain is about 72 amino acid residues long and contains the conserved binding motif GMTCXXC, of which the cysteines are involved in the copper coordination. Studies have shown that the protein binds six copper atoms suggesting the potential involvement of each metal-binding domain. Separate functional roles for the latter domains have been …

Rhizopine Synthesis – Potential Mediators For Nitrogen Fixation In Legume Plants, Venkat Reddy Guduru

Masters Theses

This research project focused on novel and efficient synthetic approaches of inosamine derivatives (rhizopines). The preparation of specific rhizopines would help elucidate the microbial pathway of rhizopine catabolism and degradation, and determine the role of corresponding genes during nitrogen fixation. We have investigated regio - and stereoselective transformations of myo-inositol derivative 28 utilizing an organostannane as key intermediate towards rhizopine 1a. The synthesis involved several protection and deprotection strategies to control competing reactivities of six hydroxyl groups of myo-inositol. Rhizopine 1a was prepared efficiently as a single isomer in 8 steps and 13% yield by controlling reactions …

Effect Of Antioxidants On Cadmium Induced Oxidative Stress And Signal Transduction, Deepti Goel

Masters Theses

A study was done to establish if reactive oxygen species (ROS) participate in the signal transduction pathway through which cadmium induces gene transcription. Cadmium has become a concern in the health care community in the past few years as evidence suggests that cadmium can induce the development of tumors, influence cell signaling and cause damage to organs, tissue, cells and DNA. The mechanism by which cadmium exerts its action on cellular processes or induces toxicity is however unclear although there is evidence to suggest that ROS play a role. Our laboratory is interested in understanding the mechanisms of differentially regulated …

Synthesis Of Cyclopropanes Via Organoiron Methodology: Preparation And Rearrangement Of Divinylcyclopropanes, Nathaniel J. Wallock, William A. Donaldson

Chemistry Faculty Research and Publications

Addition of alkenyl Grignard reagents to (1-methoxycarbonylpentadienyl)iron(1+) cation generates the corresponding (2-alkenylpent-3-en-1,5-diyl)iron complexes. Oxidatively induced-reductive elimination of these complexes gives divinylcyclopropanes which can undergo subsequent Cope rearrangement to give 1,4-cycloheptadienes.

11-(2,2-Dimethylpropyl)-12-{2-[12-(2,2-Dimethylpropyl)- 9,10-Dihydro-9,10-Ethenoanthracen-11-Yl]- Ethyl}-9,10-Dihydro-9,10-Ethenoanthracene, Joseph P. Herres, Mark A. Forman, Kraig A. Wheeler, Glenn P.A. Yap

Faculty Research and Creative Activity

Reaction of tert-butyllithium with 11,12-dimethylene-9,10- dihydro-9,10-ethanoanthracene and 4,5-diiodopentacyclo- [4.3.0.02,4.03,8.05,7]nonane gives three products, one of which crystallizes from petroleum ether as the title compound, C44H46, (I). Molecules of (I) are positioned on inversion centers (Z0 = 0.5) in the space group P21/n and lack any discernible intermolecular interactions.

How To Choose One-Dimensional Basis Functions So That A Very Efficient Multidimensional Basis May Be Extracted From A Direct Product Of The One-Dimensional Functions: Energy Levels Of Coupled Systems With As Many As 16 Coordinates, Richard Dawes, Tucker Carrington Jr.

Chemistry Faculty Research & Creative Works

In this paper we propose a scheme for choosing basis functions for quantum dynamics calculations. Direct product bases are frequently used. The number of direct product functions required to converge a spectrum, compute a rate constant, etc., is so large that direct product calculations are impossible for molecules or reacting systems with more than four atoms. It is common to extract a smaller working basis from a huge direct product basis by removing some of the product functions. We advocate a build and prune strategy of this type. the one-dimensional (1D) functions from which we build the direct product basis …

Strongly Decoupled Europium And Iron Vibrational Modes In Filled Skutterudites, Gary J. Long, Raphäel P. Hermann, Fernande Grandjean, Ercan E. Alp, Wolfgang Sturhahn, Charles E. Johnson, Dennis E. Brown, Olaf Leupold, Rudolf Rüffer

Chemistry Faculty Research & Creative Works

The europium partial vibrational density of states (DOS) in EuFe₄Sb₁₂ and the iron partial vibrational DOS in both EuFe₄Sb₁₂ and Ce⁵⁷Fe₄Sb₁₂ have been obtained by nuclear inelastic scattering. The results reveal the strong independence of the iron and rare-earth vibrational modes. The cage filling europium only participates significantly to the low-energy local vibrational modes. The force constants have been obtained from the measured probability of nuclear absorption. The energies of the peaks in the europium and iron DOS are in excellent agreement with the calculated DOS in LaFe_{4 …}

Controlling The Morphology Of Composite Latex Particles, Douglas Holmes

Inquiry Journal 2005

No abstract provided.

The Synthesis Of Chiral Lactones From Racemic -Hydroxyamides Using The Amidase From Brevibacterium Sp. Strain R312, Thomas Goyne, Jennifer Yamaoka, Matthew Pridgeon, Kyle Miner, Stephen Taylor, Min-Ken Liao

Thomas Goyne

No abstract provided.

Using A Microplate Reader To Add A ‘Taste Of Research’ To An Undergraduate Biochemistry Teaching Laboratory, Thomas Goyne, Kasey Hammond, Kevin Mccusker, Jacob Riehm

Thomas Goyne

No abstract provided.

Evaluation Of Fluorapatite As A Waste-Form Material: First Quarter Report, January 1 - March 31, 2005, Dennis W. Lindle, Oliver Hemmers

Separations Campaign (TRP)

Fluorapatite, fluorinated calcium phosphate, has been identified as a potential matrix for the entombment of the zirconium fluoride fission product waste stream from the proposed FLEX process. If the efficacy of fluorapatite-based waste-storage can be demonstrated, then new and potentially more-efficient options for handling and separating high-level wastes, based on fluoride-salt extraction, will become feasible. This proposal will develop a dual-path research project to develop a process to fabricate a synthetic fluorapatite waste form for the ZrF₄, FP waste stream, characterize the waste form, examine its performance under environmental conditions, and correlate the behavior of the waste form …

Determining The Optimal Size Of Small Molecule Mixtures For High Throughput Nmr Screening, Kelly A. Mercier, Robert Powers

Robert Powers Publications

High-throughput screening (HTS) using NMR spectroscopy has become a common component of the drug discovery effort and is widely used throughout the pharmaceutical industry. NMR provides additional information about the nature of small molecule-protein interactions compared to traditional HTS methods. In order to achieve comparable efficiency, small molecules are often screened as mixtures in NMR-based assays. Nevertheless, an analysis of the efficiency of mixtures and a corresponding determination of the optimum mixture size (OMS) that minimizes the amount of material and instrumentation time required for an NMR screen has been lacking. A model for calculating OMS based on the application …

Alterations In Uterine And Placental Sodium Pump Abundance May Contribute To The Onset Of Mouse Labor, Carlos Jacob Vance

Theses and Dissertations

Objective: Reductions in sodium pump (SP) abundance can give rise to increases in contractile force in uterine and vascular smooth muscle as well as an increased secretion in secretory cells, including potentially those of the placenta. To determine whether the mouse might serve as a model for human pregnancy in terms of the SP and to determine whether changes in SP abundance anticipate or follow labor, we studied pregnant mice over the final trimester of their pregnancy.

Study Design: C57Bl6 dams (n=46) were bred and studied during their pregnancy. Animals (n=4) were sacrificed at specific gestational time points. Other mice …

Ion Transmission In The First Vacuum Stage Of An Inductively Coupled Plasma Mass Spectrometer, Jeffrey Harris Macedone

Theses and Dissertations

The inductively coupled plasma mass spectrometer (ICP-MS) is the instrument of choice for trace and ultra-trace elemental analysis. However, the ICP-MS suffers from matrix effects. Matrix effects occur when instrument response varies as the composition of the sample matrix is changed. Matrix effects, or non-spectroscopic interferences, limit the accuracy of routine analysis. Identification of the sources of matrix effects provide a basis for reducing or eliminating them. As inaccuracies in the ICP-MS are more severe than those in the ICP atomic emission spectrometer, the problem may be due, at least in part, to the vacuum interface used to couple the …

Semiclassical Nonadiabatic Dynamics With Quantum Trajectories, Vitaly A. Rassolov, Sophya V. Garashchuk

Faculty Publications

Dynamics based on quantum trajectories with approximate quantum potential is generalized to nonadiabatic systems and its semiclassical properties are discussed. The formulation uses the mixed polar-coordinate space representation of a wave function. The polar part describes the overall time evolution of the wave-function components semiclassically using the single-surface approximate quantum potential. The coordinate part represents a complex“population” amplitude, which in case of localized coupling can be solved for quantum mechanically in an efficient manner. In the high-energy regime this is accomplished by using a small basis determined by the coupling between surfaces. An illustration is given for a typical curve-crossing …

Clean, High-Yield Preparation Of S,S- And R,S- Amino Acid Isosteres, Aslam A. Malik, Todd E. Clement, Hasan Palandoken, James Robinson Iii, Joy A. Stringer

Chemistry and Biochemistry

The present invention provides compounds and methods that can be used to convert the intermediate halomethyl ketones (HMKs), e.g., chloromethyl ketones, to the corresponding S,S- and R,S-diastereomers. More particularly, the present invention provides: (1) reduction methods; (2) inversion methods; and (3) methods involving the epoxidation of alkenes. Using the various methods of the present invention, the R,S-epoxide and the intermediary compounds can be prepared reliably, in high yields and in high purity.

Site-Specific And Synergistic Stimulation Of Methylation On The Bacterial Chemotaxis Receptor Tsr By Serine And Chew, Robert Weis

Robert Weis

Background Specific glutamates in the methyl-accepting chemotaxis proteins (MCPs) of Escherichia coli are modified during sensory adaptation. Attractants that bind to MCPs are known to increase the rate of receptor modification, as with serine and the serine receptor (Tsr), which contributes to an increase in the steady-state (adapted) methylation level. However, MCPs form ternary complexes with two cytoplasmic signaling proteins, the kinase (CheA) and an adaptor protein (CheW), but their influences on receptor methylation are unknown. Here, the influence of CheW on the rate of Tsr methylation has been studied to identify contributions to the process of adaptation. Results Methyl …

Screening Of Pharmaceuticals And Other Pollutants Of Concern By A Combination Of Chemical And Biological Methods, Arlette Azua

FIU Electronic Theses and Dissertations

This study examined the occurrence of pharmaceuticals and personal care products (PPCP's) in surface waters of Florida and their potential to be use as indicators of wastewater contamination. Previous studies have shown that elimination of pharmaceuticals in municipal sewage treatment plants is often incomplete. Aquatic ecosystems are under increased stress from human activities, particularly in heavily populated areas. The purpose of this study was to find an ideal indicator for wastewater. The applied methods, GC/MS and LC/MS, were suitable for the determination of pharmaceuticals and personal care products in aqueous environmental samples to the lower parts-per-trillion (ng/L) level. As a …

Reconstitution Of A Minimal Dna Replicase From Pseudomonas Aeruginosa And Stimulation By Non-Cognate Auxiliary Factors, Thale C. Jarvis, Amber A. Beaudry, James M. Bullard, Nebojsa Janjic, Charles S. Mchenry

Chemistry Faculty Publications and Presentations

DNA polymerase III holoenzyme is responsible for chromosomal replication in bacteria. The components and functions of Escherichia coli DNA polymerase III holoenzyme have been studied extensively. Here, we report the reconstitution of replicase activity by essential components of DNA polymerase holoenzyme from the pathogen Pseudomonas aeruginosa. We have expressed and purified the processivity factor (β), single-stranded DNA-binding protein, a complex containing the polymerase (α) and exonuclease (ϵ) subunits, and the essential components of the DnaX complex (τ₃δδ′). Efficient primer elongation requires the presence of αϵ, β, and τ₃δδ′. Pseudomonas aeruginosa αϵ can substitute completely for …

Size-Driven Domain Reorientation In Hydrothermally Derived Lead Titanate Nanoparticles, Zhiyuan Ye, Elliot B. Slamovich, Alexander H. King

Alexander H. King

High-resolution transmission electron microscopy studies of hydrothermally derived platelike lead titanate nanoparticles reveal that below a critical size of approximately 70 nm, the single ferroelectric domain polarization axis reorients from perpendicular to parallel to the plate. We suggest that during particle growth, ions in the hydrothermal processing medium compensate for the ferroelectric depolarization energy. When the processing medium is removed by washing and drying, single domain nanoparticles minimize their depolarization energy by c-axis flipping.

Simulations Of Proton Order And Disorder In Ice Ih, Steven W. Rick

Chemistry Faculty Publications

Computer simulations of ice Ih with different proton orientations are presented. Simulations of proton disordered ice are carried out using a Monte Carlo method which samples over proton degree of freedom, allowing for the calculation of the dielectric constant and for the examination of the degree of proton disorder. Simulations are also presented for two proton ordered structures of ice Ih, the ferroelectric Cmc2₁ structure or ice XI and the antiferroelectric Pna2₁ structure. These simulations indicate that a transition to a proton ordered phase occurs at low temperatures (below 80 K). The …

Magnetic Characterization Of Nanocrystalline Nickel Ferrite Films Processed By A Spin-Spraying Method, Gabriel Caruntu, I Dumitru, Bush Gg, Daniela Caruntu, Charles J. O'Connor

Chemistry Faculty Publications

Highly crystalline nickel ferrite films with different chemical compositions were processed via the spin-spraying method and their morphological, structural and magnetic properties were subsequently investigated. Regardless of the chemical composition, films with variable thicknesses are constructed by 200–400 nm spherical grains grown in the direction normal to the substrate surface. Magnetization measurements show that the spinel ferrite films present a hysteretic behaviour at room temperature with a randomly oriented in-plane easy axis and an anisotropy constant K1 ≈ −2.5 × 104 erg cm−3 Furthermore, the absence of an angular dependence of the coercivity for the in-plane measurement of …

Fundamental Chemistry Of U And Pu In The Tbp-Dodecane-Nitric Acid System: Quaterly Report January - March, 2005, Kenneth Czerwinski, Cynthia-May Gong, Amber Wright

Separations Campaign (TRP)

The speciation of hexavalent U and tetravalent Pu will be examined in the TBP-dodecane-nitric acid systems. This topic is chosen based on data needs for separation modeling identified by the AFCI. Emphasis will be placed on studying the influence of nitrate and acetohydroxamic acid on U and Pu speciation as well as conditions where a third phase forms in the organic phase. The organic phase will be 30% TBP in dodecane. Equal volumes of aqueous and organic phase will be used. The speciation of the actinides in the aqueous and organic phase will be determined by a number of different …

Fundamental Chemistry Of U And Pu In The Tbp-Dodecane-Nitric Acid System: Quarterly Report January - March, 2006, Amber Wright, Frederic Poineau, Kenneth Czerwinski

Separations Campaign (TRP)

The speciation of hexavalent U and tetravalent Pu will be examined in the Tributylphosphate (TBP)-dodecane-nitric acid systems. This topic is chosen based on data needs for separation modeling identified by the AFCI. Emphasis will be placed on studying the influence of nitrate and acetohydroxamic acid on U and Pu speciation as well as conditions where a third phase forms in the organic phase. The organic phase will be 30% TBP in dodecane. Equal volumes of aqueous and organic phase will be used. The speciation of the actinides in the aqueous and organic phase will be determined by a number of …