Chemistry Commons^™

The Material Properties Of Cssnbr3 And Csbr:Sn-1% And Their Potential As Scintillator Detector Material, Neal B. Kleinschmidt

Theses and Dissertations

The search for superior nuclear radiation detection materials is ongoing. Current scintillator materials using Thallium doped Sodium Iodide or Cesium Iodide are the benchmarks for ease of use and quick identification of isotope species. This research aims to explore Cesium Bromide doped with 1% molar tin (CsBr:Sn-1%) and Cesium Tin Bromide (CsSnBr₃) as candidate materials for a new scintillator. The techniques of Extended X-Ray Absorption Fine Structure (EXAFS), X-Ray Absorption Near Edge Structure (XANES) and Cathodoluminescence are used to determine the suit- ability of CsSnBr3 and CsBr:Sn-1% with Sn⁴⁺ as a potential scintillator materials and explore their …

Atomic Details Of Near-Transition State Conformers For Enzyme Phosphoryl Transfer Revealed By Mgf3− Rather Than By Phosphoranes, Nicola J. Baxter, Matthew W. Bowler, Tooba Alizadeh, Matthew J. Cliff, Andrea M. Hounslow, Bin Wu, David B. Berkowitz, Nicholas H. Williams, G. Michael Blackburn, Jonathan P. Waltho

David Berkowitz Publications

Prior evidence supporting the direct observation of phosphorane intermediates in enzymatic phosphoryl transfer reactions was based on the interpretation of electron density corresponding to trigonal species bridging the donor and acceptor atoms. Close examination of the crystalline state of β-phosphoglucomutase, the archetypal phosphorane intermediate-containing enzyme, reveals that the trigonal species is not PO−3 , but is MgF−3 (trifluoromagnesate). Although MgF−3 complexes are transition state analogues rather than phosphoryl group transfer reaction intermediates, the presence of fluorine nuclei in near-transition state conformations offers new opportunities to explore the nature of the interactions, in particular the independent measures of local electrostatic and …

Depositional Ice Nucleation On Solid Ammonium Sulfate And Glutaric Acid Particles, K. J. Baustian, M. E. Wise, M. A. Tolbert

CUP Faculty Research

Heterogeneous ice nucleation on solid ammonium sulfate and glutaric acid particles was studied using optical microscopy and Raman spectroscopy. Optical microscopy was used to detect selective nucleation events as water vapor was slowly introduced into an environmental sample cell. Particles that nucleated ice were dried via sublimation and examined in detail using Raman spectroscopy. Depositional ice nucleation is highly selective and occurred preferentially on just a few ammonium sulfate and glutaric acid particles in each sample. For freezing temperatures between 214 K and 235 K an average ice saturation ratio of S = 1.10±0.07 for solid ammonium sulfate was observed. …

Reactive Layer-By-Layer Assembly Of Suspended Thin Films And Semipermeable Membranes At Interfaces Created Between Aqueous And Organic Phases, Maren E. Buck, David M. Lynn

Chemistry: Faculty Publications

Thin films of polymer suspended across the openings of pores, channels, and microcavities are of interest in a broad range of fundamental and applied contexts. A "reactive" layer-by-layer approach Is demonstrated for the fabrication of suspended thin films and semipermeable membranes that makes use of liquid/ liquid interfaces created between immiscible aqueous and organic phases as templates for film fabrication (see image). (Figure Presented).

Roles Of Serine 101, Histidine 310 And Valine 464 In The Reaction Catalyzed By Choline Oxidase From Arthrobacter Globiformis, Steffan Finnegan

Chemistry Dissertations

The enzymatic oxidation of choline to glycine betaine is of interest because organisms accumulate glycine betaine intracellularly in response to stress conditions, as such it is of potential interest for the genetic engineering of crops that do not naturally possess efficient pathways for the synthesis of glycine betaine, and for the potential development of drugs that target the glycine betaine biosynthetic pathway in human pathogens. To date, one of the best characterized enzymes belonging to this pathway is the flavin-dependent choline oxidase from Arthrobacter globiformis. In this enzyme, choline oxidation proceeds through two reductive half-reactions and two oxidative half-reactions. In …

Time-Resolved Infrared Spectroscopy And Density Functional Theory Study Of Weak Interactions Of Metal Carbonyls And Organic Solvents, Carolyn Evans Sheffield

Theses and Dissertations

Pulsed laser flash photolysis of M(CO)6 (M = Cr, W) in cyclohexane with a small amount of benzene results in three sequential reactions. The first is the photodissociation of the parent to yield a M(CO)5:C6H12 complex, which takes place faster than the time resolution of our experiments. The second reaction is the replacement of the cyclohexane ligand with benzene to form a M(CO)5:C6H6 complex, in which benzene is coordinated to the metal via one side of the ring. This complex then falls apart in solution as M(CO)5 coordinates with a trace impurity in the solution that is likely water. Kinetic …

Metals: Typical And Less Typical, Transition And Inner Transition, Fathi Habashi

Fathi Habashi

While most chemists agree on what is a metal and what is a non-metal there is a disagreement with respect to what is a metalloid and what is a transition metal. It is believed that this problem can be solved if two new terms are adopted: typical and less typical metals. These new terms will also help reconcile the European Periodic Table versus the North American regarding numbering of groups as well as the IUPAC numbering which could be as well abandoned in favour of group names as will be shown in the manuscript.

An Electrochemical Cell For The Efficient Turn Around Of Wafer Working Electrodes, Nicholas Wozniak, Alyssa Frey, Lucas Osterbur, Timothy Boman, Jennifer R. Hampton

Faculty Publications

We present a new design for an electrochemical cell for use with wafer working electrodes. The key feature of the design is the use of half turn thumb screws to form a liquid-tight seal between an o-ring and the sample surface. The assembly or disassembly of the cell requires a half turn of each thumb screw, which facilitates the quick turn around of wafer samples. The electrochemical performance of the cell is demonstrated by cyclic voltammetry and double step chronoamperometry measurements of the ferricyanide/ferrocyanide couple.

Utilizing Service Learning In The Analytical Chemistry Classroom, Kimberly D. Chichester, Colleen Dugan, Amanda Lewis, Maryann Herman, Irene Kimaru

Chemistry Faculty/Staff Publications

Service learning has been incorporated into the Analytical Chemistry Laboratory to give students a real world sampling experience including both soil and water, alongside professionals in their fields. Analysis of the soil and water includes metals, suspended solids, phosphorus and nitrogen containing compounds requiring knowledge of several different instrumental and wet chemical techniques. Most educational experiences do not afford students the chance to see the real world applications of their classroom knowledge, but with the service learning aspects this deficiency has been resolved. In the soil experience, students provide homeowners from the Highland Park and South Wedge neighbors with lead …

Quasispecies-Like Behavior Observed In Catalytic Rna Populations Evolving In A Test Tube, Carolina Diaz Arenas, Niles Lehman

Chemistry Faculty Publications and Presentations

Background: During the RNA World, molecular populations were probably very small and highly susceptible to the force of strong random drift. In conjunction with Muller's Ratchet, this would have imposed difficulties for the preservation of the genetic information and the survival of the populations. Mechanisms that allowed these nascent populations to overcome this problem must have been advantageous.

Results: Using continuous in vitro evolution experimentation with an increased mutation rate imposed by MnCl2, it was found that clonal 100-molecule populations of ribozymes clearly exhibit certain characteristics of a quasispecies. This is the first time this has been seen …

Nuclear Quantum Effects In The Structure And Lineshapes Of The N2 Near-Edge X-Ray Absorption Fine Structure Spectrum, Shervin Fatehi, Craig P. Schwartz, Richard J. Saykally, David Prendergast

Chemistry Faculty Publications and Presentations

We study the relative ability of several models of x-ray absorption spectra to capture the Franck–Condon structure apparent from an experiment on gaseous nitrogen. In doing so, we adopt the Born–Oppenheimer approximation and a constrained density functional theory method for computing the energies of the x-ray-excited molecule. Starting from an otherwise classical model for the spectrum, we systematically introduce more realistic physics, first by substituting the quantum mechanical nuclear radial density in the bond separation R for the classical radial density, then by adding the effect of zero-point energy and other level shifts, and finally by including explicit rovibrational quantization …

Intermolecular Dehydrative Coupling Reaction Of Arylketones With Cyclic Alkenes Catalyzed By A Well-Defined Cationic Ruthenium-Hydride Complex: A Novel Ketone Olefination Method Via Vinyl C–H Bond Activation, Chae S. Yi, Do W. Lee

Chemistry Faculty Research and Publications

The cationic ruthenium−hydride complex [(η⁶-C₆H₆)(PCy₃)(CO)RuH]⁺BF₄⁻ was found to be a highly effective catalyst for the intermolecular olefination reaction of aryl ketones with cycloalkenes. The preliminary mechanistic analysis revealed that an electrophilic ruthenium−vinyl complex is the key species for mediating both vinyl C−H bond activation and the dehydrative olefination steps of the coupling reaction.

Microscopic And Spectroscopic Studies Of Thermally Enhanced Electrospun Pmma Micro- And Nanofibers, Sean Pelfrey, Travis Cantu, Michael R. Papantonakis, Duane L. Simonson, R. Andrew Mcgill, Javier Macossay-Torres

Chemistry Faculty Publications and Presentations

Carbon nanofibers (CNFs) have been incorporated into poly(methyl methacrylate) (PMMA) through electrospinning. The resulting micro- and nanofibers have been characterized by Scanning Electron Microscopy (SEM), which confirmed fiber formation and demonstrated a core-sheath structure of the PMMA fibers. Thermogravimetric Analysis (TGA) was used to obtain the thermal properties of the materials, indicating an enhancement in the thermal properties of the composite fibers. In addition, Fourier Transform Infrared Spectroscopy (FTIR) was utilized to investigate the interactions of PMMA micro- and nanofibers with CNFs, demonstrating the preferred sites of intermolecular interactions between the polymer matrix and the filler.

Targeting Prostate Cancer Cells In Vivo Using A Rapidly Internalizing Novel Human Single-Chain Antibody Fragment., Arun K. Iyer

Arun Iyer

Human antibodies targeting prostate cancer cell surface epitopes may be useful for imaging and therapy. The objective of this study was to evaluate the tumor targeting of an internalizing human antibody fragment, a small-size platform, to provide high contrast in a mouse model of human prostate carcinoma. METHODS: A prostate tumor-targeting single-chain antibody fragment (scFv), UA20, along with a nonbinding control scFv, N3M2, were labeled with (99m)Tc and evaluated for binding and rapid internalization into human prostate tumor cells in vitro and tumor homing in vivo using xenograft models. For the in vitro studies, the labeled UA20 scFv was incubated …

Beethoven: Patriotism And Social Justice, Fathi Habashi

Fathi Habashi

The Synthesise Of Electron-Conducting Redox Hydrogel And Its Application In Microbial Fuel Cell, Kai-Peng Wang, Sheng-Li Chen

Journal of Electrochemistry

Efficient electron transfer between the microbe and the anode is key for the electricity generation in Microbial fuel cell(MFC).Through the modification of anode,the rate of electron transfer can be accelerated,therefore the performance of MFC can be enhanced.In this paper,we report the synthesis of a type of electronconducting and bio-compatible redox hydrogel and its application.The hydrogel consists of poly(4-vinylpyridine) as backbone and neutral red as the redox center.By immobiliazing neutral red on the backbone through covalent bond,the secondary contamination due to the soluble redox mediator to external environment can be prevented.MFCs using the hydrogel-modified carbon anode significantly exhibit shorter acclimation period,and …

Preparation And Electrochemical Behavior Of Li_4ti_5o_(12) Nanosheets As Anode Material For Lithium Ion Battery, Yi-Fei Wang, Yu-Feng Tang, Zheng Qiu, Li Yang

Journal of Electrochemistry

Spinel lithium titanate(Li4Ti5O12) nanosheets with a size range of 200 ～400 nm were synthesized by hydrothermal process from the amorphous hydrous titanium oxide precursors.The as-prepared products were characterized by X-ray powder diffraction(XRD),scanning electron microscopy(SEM) and transmission electron microscopy(TEM).The electrochemical behaviors of Li4Ti5O12 electrode in conventional organic electrolyte and ionic liquid electrolyte were investigated by using cyclic voltammetry,galvanostatic charge-discharge and AC impedance techniques.The experimental results indicate that the as-prepared nanostructured Li4Ti5O12,evaluated as anode material,exhibited good reversibility and cycle performance.It is expected to be a potential anode material for commerical battery applications.

Selective Regulation Of Aromatase Expression For Drug Discovery, Robert W. Brueggemeier, Bin Su, Michael V. Darby, Yasuro Sugimoto

Chemistry Faculty Publications

Aromatase is a particularly attractive drug target in the treatment of hormone-responsive breast cancer, and aromatase activity in breast cancer patients is greater in or near the tumor tissue compared with the normal breast tissue. Complex regulation of aromatase expression in human tissues involves alternative promoter sites that provide tissue-specific control. Previous studies in our laboratories suggested a strong association between aromatase (CYP19) gene expression and the expression of cyclooxygenase (COX) genes. Additionally, COX selective inhibitors can suppress CYP19 gene expression and decrease aromatase activity. Our current hypothesis is that pharmacological regulation of aromatase can act locally to decrease the …

Applications Of Block Copolymer Films In The Field Of Electrochemical Energy Systems, Jing-Ze Li, Guo-Guang Chen, Di Mei, Wei Zou, Jian-Wen Li, Motonori Komura, Tomokazu Iyoda

Journal of Electrochemistry

A new series of amphiphilic liquid crystalline block copolymer thin films,having normally aligned and highly ordered nanocylinder array,were functionalized as anisotropic ion conducting materials by selectively infiltration.These ion-active nanocylinders are coaxially aligned and hexagonally arranged in a large area,which might be used as novel types of electrolyte films for electrochemical energy systems such as lithium ion battery,fuel cell,etc.Since the ordered cylinders can carry on and store the ions,the block copolymer films can be utilized as the advanced template to fabricate the ordered array of nanoporous,nanoparticles,and nanowires for the potential application in lithium ion battery as three dimensional electrode materials.

The Electrochemical Characteristics Of Cpo-Pll/Gc Electrode, Wen Zhao, Xia-Qin Wu, Zhong-Qing Lu, Wen-Jing Hou, He-Xing Li

Journal of Electrochemistry

Poly-L-lysine(PLL) was electropolymerized onto the surface of glassy carbon(GC) electrode.1[(3-dimethylamino)propyl]-3-ethylcarbodiimide hydrochloride(EDC) was used as a Cross-linking agent to immobilized Chloroperoxidase(CPO) onto the PLL/GC electrode.A pair of well-defined redox peaks was observed at CPO-PLL/GC electrode,which clearly suggested that PLL can promote the direct electron transfer between the CPO and the GC electrodes.The cyclic voltammetry results also showed that the electron transfer at CPO-PLL/GC is a surface adsorption-controlled quasi-reversible process,which is accompanied with proton transfer.The CPO-PLL/GC electrode exhibited a good electrochemical stability and excellently electrocatalytic activity for electrochemical reduction of O2.