Physical Sciences and Mathematics Commons^™

Cation Occupancy Determination In Manganese Zinc Ferrites Using Fourier Transform Infrared Spectroscopy, M. D. Shultz, E. E. Carpenter, S. A. Morrison, S. Calvin

Chemistry Publications

The magnetic and electric properties of ferrites are influenced by the cation distribution within the crystalline spinel lattice. Methods such as extended x-ray-absorption fine structure(EXAFS) have been used to determine cation occupancies within the crystalline structure of materials such as manganesezincferrite (MZFO); however, it is not practical to be used for daily analysis. Fourier transform infrared (FTIR)spectroscopy is another technique which has the potential to determine cation occupancy while offering speed and convenience. In the literature it has been demonstrated that in ferrite systems FTIR data can be correlated to cation percentages when comparing tetrahedral (Td) and octahedral (Oh) sites. …

Orientational Correlations In Liquid Acetone And Dimethyl Sulfoxide: A Comparative Study, Sylvia E. Mclain, Alan K. Soper, Alenka Luzar

Chemistry Publications

The structure of acetone and dimethyl sulfoxide in the liquid state is investigated using a combination of neutron diffractionmeasurements and empirical potential structure refinement (EPSR) modeling. By extracting the orientational correlations from the EPSR model, the alignment of dipoles in both fluids is identified. At short distances the dipoles or neighboring molecules are found to be in antiparallel configurations, but further out the molecules tend to be aligned predominately as head to tail in the manner of dipolar ordering. The distribution of these orientations in space around a central molecule is strongly influenced by the underlying symmetry of the central …

Stability Of Warfarin Solutions For Drug–Protein Binding Measurements: Spectroscopic And Chromatographic Studies, Annette C. Moser, Charles A. Kingsbury, David S. Hage

Chemistry Department: Faculty Publications

Warfarin is commonly used in drug–protein binding studies as a displacement marker for Sudlow site I on the protein human serum albumin (HSA). This study examined the stability of aqueous warfarin solutions prepared for such experiments. This was investigated using NMR spectroscopy and affinity chromatography. It was found by 1H NMR that warfarin underwent a slow first-order conversion in aqueous solution. The rate of this reaction increased with temperature, giving rate constants at pH 7.4 of 0.0086 h⁻¹ at 25 °C and 0.041 h⁻¹ at 37 °C. It was concluded from further 1H and 13C NMR studies, along …

1,1´-Diethyl-2,2´,3,3´,4,4´,5,5´-Octamethylferrocenium Tetracyanoethylenide, [Fe(C5etme4)2]+[Tcne]–, A Charge-Transfer Salt Magnetic Solid With A Novel Structural Motif, T. David Harris, Michael Castellani, Arnold L. Rheingold, William M. Reiff, Gordon T. Yee

Chemistry Faculty Research

1,1′-Diethyl-2,2′,3,3′,4,4′,5,5′-octamethylferrocene has been utilized as a one-electron donor in the synthesis of a tetracyanoethylene charge-transfer salt, [Fe(C₅EtMe₄)₂]⁺[TCNE]⁻. Structural characterization shows that it adopts an arrangement of anions and cations completely different from the usual π stacking seen in analogous decamethylferrocenium compounds. The TCNE radical sits along side of the ferrocene, nearly perpendicular to the planes of the C₅ rings. The nearly square geometry of the TCNE anion creates disorder over two orientations. [Fe(C₅EtMe₄)₂]⁺[TCNE]⁻ is a simple paramagnet exhibiting neither long-range …

Solution And Solid State Interactions Between Ionic Π-Systems, Jing Chen

University of Kentucky Doctoral Dissertations

Although attractive interactions between π systems (π-π interaction) have been known for many years, understanding of its origin is still incomplete. Quantitative measuring of π-stacking is challenging due to the weak nature of the π-π interaction. This dissertation aims at elucidating a quantitative conformational analysis by NMR ring current anisotropy of an organic compound capable of intramolecular π-stacking in solution and studying charge effects on the stacking of π-systems. This dissertation offers four contributions to the area. (1) A general approach to four-state, conformational analysis based on the magnetic anisotropy of molecules undergoing fast dynamic exchange is described. (2) Study …

Projects That Assist With Content In A Traditional Organic Chemistry Course, John J. Esteb, John R. Magers, Luanne Mcnulty, Anne M. Wilson

Scholarship and Professional Work - LAS

Projects that engage undergraduate students in content-based courses, such as organic chemistry, must relate to the material and provide useful tools for the divergent needs of the students. There are few examples of these types of projects in the literature. Herein, we describe two projects, the reaction notebook and the end-of-semester synthesis activity. Each project is designed to stimulate student ownership of the material and leads to engagement with the content of the course.

Optimization Of Long Range Electron Transfer For Solar Energy, Randall H. Goldsmith

Link Foundation Energy Fellowship Reports

Organic photovoltaics have the potential to become an accessible form of alternative energy production because of their ease of manufacture via traditional printing techniques and consequent low cost.1 However, the simplicity of device manufacture belies the complex cascade of processes that allow light to be efficiently converted into electrical power.2 Electron transfer (ET) events constitute the most critical steps. ET is known to be governed by a complex function of many system-specific variables including distance, orientation, and energetics of the donor and acceptor species.3

Limited Proteolysis Of Human Histone Deacetylase 1, Nayana Kamath, Paulina Karwowska-Desaulniers, Mary Kay H. Pflum

Wayne State University Associated BioMed Central Scholarship

Abstract

Background

Histone deacetylase (HDAC) proteins are associated with cell proliferation, differentiation, apoptosis, and cancer. Specifically, HDAC1 is linked with cell growth, a hallmark of cancer formation. HDAC1 is a phosphoprotein and phosphorylation at S421 and S423 promotes HDAC1 enzymatic activity and protein association. While single and double point mutants of HDAC1 at S421 and S423 appear functionally similar, the evidence suggests that HDAC1 is phosphorylated simultaneously at both S421 and S423 in vivo. Additional experiments are necessary to probe the role of double phosphorylation of HDAC1 at S421 and S423.

Results

To characterize HDAC1 phosphorylation at S421 and S423, …

Spectroscopic Characterization Of The Ground And Low-Lying Electronic States Of Ga2n Via Anion Photoelectron Spectroscopy., S M. Sheehan, Giovanni Meloni, B F. Parsons, N Wehres, D M. Neumark

Chemistry Faculty Publications

Anion photoelectron spectra of Ga2N− were measured at photodetachment wavelengths of 416nm(2.978eV), 355nm(3.493eV), and 266nm(4.661eV). Both field-free time-of-flight and velocity-map imaging methods were used to collect the data. The field-free time-of-flight data provided better resolution of the features, while the velocity-map-imaging data provided more accurate anisotropy parameters for the peaks. Transitions from the ground electronic state of the anion to two electronic states of the neutral were observed and analyzed with the aid of electronic structure calculations and Franck-Condon simulations. The ground-state band was assigned to a transition between linear ground states of Ga2N−(XΣg+1) and Ga2N(XΣu+2), yielding the electron affinity …

Structure And Vibrational Spectra Of Mononitrated Benzo [A] Pyrenes., Kefa Karimu Onchoke, Christopher M. Hadad, Prabir K. Dutta

Faculty Publications

The molecules benzo[a]pyrene (BaP) and 1-, 3-, and 6-nitrobenzo[a]pyrene (1-NBaP, 3-NBaP, 6-NBaP) are currently of significant interest due to their presence in respirable combustion exhaust particulates and their mutagenic and carcinogenic properties. Structure−function correlations as well as spectroscopic signatures for trace analysis are necessary for these benzo[a]pyrene derivatives. In this paper, detailed infrared and Raman spectroscopic data of BaP and its three mononitrated isomers are provided for the first time. By utilizing density functional theory (DFT, B3LYP method with 6-311+G** basis set), the molecular geometries and the vibrational spectra are calculated. Good agreement is …

Truly Non Invasive Glucose Optical Sensor Based On Metal Nanoparticles Generation, Marisol Garcia

Electronic Theses and Dissertations

Diabetes is a disease that causes many complications in human normal function. This disease represents the sixth-leading cause of death in USA. Prevention of diabetes-related complications can be accomplished through tight control of glucose levels in blood. In the last decades many different glucose sensors have been developed, however, none of them are really non invasive. Herein, we present the study of the application of gold and silver nanoparticles with different shapes and aspect ratios to detect glucose traces in human fluids such as tears and sweat. This is to our knowledge the first truly non invasive glucose optical sensor, …

Sequence-Enabled Reassembly (Seer) Peptides For The Detection Of Dna Sequences, Aik T. Ooi, Cliff I. Stains, Jason R. Porter, Indraneel Ghosh, David J. Segal

Cliff Stains Publications

By combining custom zinc finger (ZF) DNA-binding technology [1,2] with protein fragment complementation [3], we have developed a technology, designated SEER (Sequence-Enabled Reassembly), that has the potential to “see” or detect genetic information within a living cell (Figure 1). These agents consist of two inactive parts of signal-generating peptides that have the ability to recognize specific DNA sequences. The two parts bind near each other in the presence of a user-defined DNA target site and generate a fluorescent signal. Two prototype SEER systems have been constructed, based on the reassembly of green fluorescent protein (SEERGFP) [4] and the enzyme β-lactamase …

The Elastic Constants And Related Properties Of The Energetic Material Cyclotrimethylene Trinitramine (Rdx) Determined By Brillouin Scattering, James J. Haycraft, Lewis L. Stevens, Craig J. Eckhardt

Craig J. Eckhardt Publications

The acoustic phonons of cyclotrimethylene trinitramine (RDX) have been studied using Brillouin scattering. The analysis of the acoustic-phonon velocities allowed determination of the complete stiffness tensor for this energetic material. The results are compared to other recent experimental and theoretical determinations of the RDX elastic constants, bulk moduli, and shear moduli. The observed ordering of elastic constants, C₁₁>C₂₂>C₃₃, is qualitatively associated with a (001) cleavage plane and molecular packing. This interpretation is further corroborated by the linear compressibilities plotted in three crystallographic planes, and a comparison to recent theoretical and experimental hydrostatic compression studies …

Performance Efficacy Using A Comparison Of Commerical And In-House Y-Str Multiplex Systems For Operational Use, Kathleen Mayntz-Press

Electronic Theses and Dissertations

It is routine for the forensic scientist to obtain a genetic profile of an individual from DNA recovered from a biological stain deposited at a crime scene. In contrast, only a limited number of laboratories in the United States have the capability of performing Y-STR analysis in casework. In order to aid in facilitating the transfer of Y-STR technology to the crime laboratory community for operational use, a comparison between commercial products from three main vendors (Applied Biosystems AmpFLSTR Yfiler PCR Amplification Kit, Promega PowerPlex - Y System, Reliagene Y-PLEX 12) and two in-house Y-STR multiplexes (MPI and MPB) commenced. …

New Developments On High-Resolution Luminescence Spectroscopy And Their Application To The Direct Analysis Of Organic Pollutants, Shenjiang Yu

Electronic Theses and Dissertations

Polycyclic aromatic compounds (PACs), which comprise a complex class of condensed multi-ring benzenoid compounds, are important environmental pollutants originating from a wide variety of natural and anthropogenic sources. PACs are generally formed during incomplete combustion of pyrolisis of organic matter containing carbon and hydrogen. Because combustion of organic materials is involved in countless natural processes or human activities, PACs are omnipresent and abundant pollutants in air, soil, and water. Chemical analysis of PACs is of great environmental and toxicological importance. Many of them are highly suspect as etiological agents in human cancer. Because PACs carcinogenic properties strongly depend on molecular …

Investigation Of Coke Deposition And Coke Inhibition By Organosulfur Compounds In The Pyrolysis Of Naphtha In The Jet Stirred Reactor System, D Salari, A Niaei, J Towfighi, P Panahi, Reza Nabavi

Seyed Reza nabavi

No abstract provided.

Textural And Fractal Properties Of Cuo/Al2o3 Catalyst Supports, Zeljko D. Cupic

Zeljko D Cupic

No abstract provided.

The Role Of Connective Tissue Growth Factor In Skeletal Growth And Development, Philadelphia University

Philadelphia University, Jordan

No abstract provided.

Posterminaries: Plain Text, Alexander H. King

Alexander H. King

You just can’t win an argument with an English professor.

Gold Nanoparticles Propulsion From Surface Fueled By Absorption Of Femtosecond Laser Pulse At Their Surface Plasmon Resonance, Wenyu Huang, Wei Qian, Mostafa A. El-Sayed

Wenyu Huang

Femtosecond laser irradiation of assembled nanoprisms on a quartz substrate at their strong absorbing surface plasmon resonance frequency causes their propulsion from the substrate. SEM and AFM show that the particles fly while keeping their prismatic shape, but they decrease in size by an amount that can be calculated assuming atomic sublimation. Several mechanisms are mentioned, but the sublimation mechanism, which rapidly builds up pressure under the particle and propels it away from substrate, is discussed in detail. From the kinetic energy given to the flying nanoparticle, an initial velocity of ∼160 m/s (∼360 miles/h) is calculated. The dependence of …

Thermal Effects On Domain Orientation Of Tetragonal Piezoelectrics Studied By In Situ X-Ray Diffraction, Wonyoung Chang, Alexander H. King, Keith J. Bowman

Alexander H. King

Thermal effects on domain orientation in tetragonal lead zirconate titanate (PZT) and lead titanate (PT) have been investigated by using in situ x-ray diffraction with an area detector. In the case of a soft PZT, it is found that the texture parameter called multiples of a random distribution (MRD) initially increases with temperature up to approximately 100 °C and then falls to unity at temperatures approaching the Curie temperature, whereas the MRD of hard PZT and PT initially undergoes a smaller increase or no change. The relationship between the mechanical strain energy and domain wall mobility with temperature is discussed.

Solid-Solid Phase Transformation Via Internal Stress-Induced Virtual Melting, Significantly Below The Melting Temperature. Application To Hmx Energetic Crystal, Valery I. Levitas, Bryan F. Henson, Laura B. Smilowitz, Blaine W. Asay

Valery I. Levitas

We theoretically predict a new phenomenon, namely, that a solid−solid phase transformation (PT) with a large transformation strain can occur via internal stress-induced virtual melting along the interface at temperatures significantly (more than 100 K) below the melting temperature. We show that the energy of elastic stresses, induced by transformation strain, increases the driving force for melting and reduces the melting temperature. Immediately after melting, stresses relax and the unstable melt solidifies. Fast solidification in a thin layer leads to nanoscale cracking which does not affect the thermodynamics or kinetics of the solid−solid transformation. Thus, virtual melting represents a new …

Nmr Studies Of Lysozyme Surface Accessibility By Using Different Paramagnetic Relaxation Probes, Andrea Bernini, Ottavia Spiga, Vincenzo Venditti, Filippo Prischi, Luisa Bracci, Angela Pui-Ling Tong, Wing-Tak Wong, Neri Niccolai

Vincenzo Venditti

Paramagnetic probes, whose approach to proteins can be monitored by nuclear magnetic resonance (NMR) studies, have been found to be of primary relevance for investigating protein surfaces' accessibility. Here, a Gd(III) neutral complex which contains two metal ions, [Gd2(L7)(H2O)2], is suggested as a paramagnetic probe particularly suited for systematic NMR investigation of protein surface accessibility, due to an expected high relaxivity and to the lack of electric charge which could favor specific interactions. Hen egg white lysozyme has been used as a model system to verify the absence of preferential approaches of this paramagnetic probe to specific protein moieties by …

Magnetic Circular Dichroism Of Ferromagnetic Co2+-Doped Zno, Kevin R. Kittilstved, J. Zhao, W. K. Liu, J. D. Bryan, D. A. Schwartz, D. R. Gamelin

Kevin R. Kittilstved

Cobalt-doped ZnO (Co2+:ZnO) films were studied by magnetic circular dichroism (MCD) spectroscopy. A broad 300 K ferromagnetic MCD signal was observed between 1.4 and 4.0 eV after exposure of paramagnetic Co2+:ZnO films to zinc metal vapor, attributed to low-energy photoionization transitions originating from a spin-split donor impurity band in ferromagnetic n-type Co2+:ZnO.

Direct Kinetic Correlation Of Carriers And Ferromagnetism In Co2+:Zno, Kevin R. Kittilstved, D. A. Schwartz, A. C. Tuan, S. M. Heald, S. A. Chambers, D. R. Gamelin

Kevin R. Kittilstved

The hypothesis that high-Curie-temperature ferromagnetism in cobalt-doped ZnO (Co2+:  ZnO) is mediated by charge carriers was tested by controlled introduction and removal of the shallow donor interstitial zinc. Using oriented epitaxial Co2+:  ZnO films grown by chemical vapor deposition, kinetics measurements demonstrate a direct correlation between the oxidative quenching of ferromagnetism and the diffusion and oxidation of interstitial zinc. These results demonstrate controlled systematic variation of a key parameter involved in the ferromagnetism of Co2+:  ZnO and, in the process, unambiguously reveal this ferromagnetism to be dependent upon charge carriers. The distinction between defect-bound and free carriers in Co2+:  ZnO …

A Molecular Salt Of Tricyanomethanide Anion And A N,N9- Dianisylphenazinium Dication: Cooperative Affects Of Methoxy…Methoxy And Cmn…N+ Intermolecular Contacts, Scott E. Mckay, Kraig A. Wheeler, Silas C. Blackstock

Kraig A. Wheeler

A molecular salt of tricyanomethanide anion and a N,N9- dianisylphenazinium dication forms extended supramolecular assemblies that consist of unusual methoxy…methoxy and CMN…N+ intermolecular contacts.

Charge Storage Model For Hysteretic Negative-Differential Resistance In Metal-Molecule-Metal Junctions, Rebecca Hoye, R. A. Kiehl, J. D. Le, P. Candra, T. R. Hoye

Rebecca Hoye, Retired

No abstract provided.

Interaction-Induced Dipole Moment Of The Ar–H2 Dimer: Dependence On The H2 Bond Length, Robert J. Hinde

Robert Hinde

We present ab initio calculations of the interaction-induced dipole moment of the Ar–H₂ van der Waals dimer. The primary focus of our calculations is on the H₂ bond length dependence of the dipole moment, which determines the intensities of both the collision-induced H₂ = 1 ← 0 fundamental band in gaseous Ar–H₂ mixtures and the dopant-induced H₂ = 1 ← 0 absorption feature in Ar-doped solid H₂ matrices. Our calculations employ large atom-centered basis sets, diffuse bond functions positioned between the two monomers, and a coupled cluster treatment of valence electron correlation; core-valence correlation …

Population Size Bias In Descendant-Weighted Diffusion Quantum Monte Carlo Simulations, G. Lee Warren, Robert Hinde

Robert Hinde

We consider the influence of population size on the accuracy of diffusion quantum Monte Carlo simulations that employ descendant weighting or forward walking techniques to compute expectation values of observables that do not commute with the Hamiltonian. We show that for a simple model system, the d-dimensional isotropic harmonic oscillator, the population size must increase rapidly with d in order to ensure that the simulations produce accurate results. When the population size is too small, expectation values computed using descendant-weighted diffusion quantum Monte Carlo simulations exhibit significant systematic biases.

Nmr Investigations Of Natural Organic Matter In Forest Ecosystems, Chris E. Johnson

Chris E Johnson

No abstract provided.