Physical Sciences and Mathematics Commons^™

Fluorescence Prediction Through Computational Chemistry, Daniel Craig Lathey

Theses, Dissertations and Capstones

With the growing demand for diverse fluorescent dyes, it is imperative to find a more efficient methodology by which to synthesize dyes. Our research group has found a computational method that can efficiently predict the optical properties of a molecule before it is synthesized. By evaluating different semi-empirical methods, we have found a way to predict the fluorescence maxima. With the new ability of Hyperchem 7.5 to geometrically optimize a molecule in an excited state, we can predict not only the absorption maxima, but we can also predict the fluorescence maxima within 25 nm of the actual fluorescence.

With this …

Temperature And Ph Dependence Of The Cyclization Of Creatine: A Study Via Mass Spectrometry, Brian J. Diamond

Theses, Dissertations and Capstones

The creatine to creatinine cyclization is of significant biological importance, providing energy for muscle cells and indicating proper renal function. From a chemical perspective, the rate at which creatine cyclizes to form creatinine has interested researchers since the late 1920s, but the cyclization is poorly understood both energetically and mechanistically. Mass spectroscopy was used to determine the rate of creatine cyclization as a function of temperature and pH. Using these values, the energetic parameters, activation energy and Arrhenius factor, were determined as a function of pH to better understand this reaction and ultimately determine the mechanistic process for this reaction. …

Reduced Macrophage Apoptosis Is Associated With Accelerated Atherosclerosis In Low-Denstiy Lipoprotein Receptor-Null Mice, Michael Sinensky, J. Liu, D. P. Thweke, Y. R. Su, M. F. Linton, S. Fazio

Faculty Publications, Biological Sciences

Objective— The majority of apoptotic cells in atherosclerotic lesions are macrophages. However, the pathogenic role of macrophage apoptosis in the development of atherosclerosis remains unclear. Elevated expression of Bax, one of the pivotal proapoptotic proteins of the Bcl-2 family, has been found in human atherosclerotic plaques. Activation of Bax also occurs in free cholesterol-loaded and oxysterol-treated mouse macrophages. In this study, we examined the effect of Bax deficiency in bone marrow-derived leukocytes on the development of atherosclerosis in low-density lipoprotein receptor-null (LDLR−/−) mice. Methods and Results— Fourteen 8-week-old male LDLR−/− mice were lethally irradiated and reconstituted with either wild-type (WT) …

Assessment Of Rarity Of The Blackmouth Shiner Notropis Melanostomus (Cyprinidae) Based On Museum And Recent Survey Data, Martin O'Connell

Earth and Environmental Sciences Faculty Publications

Accurate knowledge of an organism's distribution is necessary for conserving species with small or isolated populations. A perceived rarity may only reflect inadequate sampling effort and suggest the need for more research. We used a recently developed method to evaluate the distribution of a rare fish species, the blackmouth shiner Notropis melanostomus Bortone 1989 (Cyprinidae), which occurs in disjunct populations in Mississippi and Florida. Until 1995, N. melanostomus had been collected from only three localities in Mississippi, but in 1995, eight new localities were discovered. We analyzed museum records of fish collections from Mississippi, Florida, and Alabama to compare sampling …

Part I : Isolation Of Dipentyl 2-(4-(Pentan-3-Yl) Phenyl) Malonate From Sanguisorba Officinalis Labill Part Ii: Synthesis Of A Novel Family Of Ethers Of Podocarpic Acid, Manjeera Yalavarty

Electronic Theses and Dissertations

The goal of part I of this thesis was to isolate pure anti cancer compounds from the Russian plant Sanguisorba officinalis. This plant was selected for investigation because it showed 100% activity against leukemia (L1210 mouse leukemia cells) during the preliminary screening of approximately 100 Russian plant extracts. This work has resulted in the isolation of novel compound 11 using traditional chromatography techniques. Compound 11 was characterized with spectroscopic techniques such as IR, 1H NMR, 13C NMR, DEPT, DQCOSY and MS. Compound 11 was assigned the structure dipentyl 2-(4-(pentan-3-yl) phenyl) malonate. The goal of part II of this thesis was …

Differential Tethering Of Log Phase Trypanosoma Brucei Onto Chemically Distinct Surfaces, Darrell R. Fry, Lydia Archuleta, Ashley Dunham, Justin Rains

Faculty Publications

Our long-term objective is to understand and model the motility of T. brucei. Obtaining high quality images of T. brucei that allow one to differentiate between cell body movement and flagallar movement is difficult with T. brucei because the flagellum is attached along the cell body. Currently, our approach his to tether T. brucei onto a microscope friendly surface. The contributions to the ISIS our progress to date. Specifically, we look at the adhesion density of T. brucei to numerous microscope friendly surfaces and at the optimum adhesion conditions for T. brucei.

Phase Transition In Single Crystal Cs2nb4o11, Jianjun Liu, E. P. Kharitonova, Chun-Gang Duan, Wai-Ning Mei, Robert W. Smith, John R. Hardy

Physics Faculty Publications

We studied temperature dependence of complex capacitance, impedance, and polarized Raman spectra of single crystal Cs₂Nb₄O₁₁. First, we observed a sharp λ-shaped peak at 165 °C in the complex capacitance, then found drastic changes in the Raman spectra in the same temperature range. Utilizing the pseudosymmetry search of structure space group, we attributed the observed anomalies to a structural change from the room temperature orthorhombic Pnn2 to another orthorhombic Imm2. We also measured room temperature polarized Raman spectra in different symmetries of normal vibrations and assigned high wavenumber Raman bands to the …

(Μ-Diazenediyldiphenyl-Κ2c2, N2: Κ2c2′, N1) Bis [(3, 5-Dimethylphenyl) Tellurium (Ii)]., Prabodhika R. Mallikaratchy, Richard E. Norman, Frank R. Fronczek, Thomas Junk

Publications and Research

The title compound, C28H26N2Te2, prepared by reduction of (3,5-dimethylphenyl)(2-nitrophenyl)tellurium(II), is the first structurally characterized example of an azo group bridging two TeII centers. The compound is centrosymmetric and the Te—N distance [2.6916 (19) A ° ] is longer than in non-bridging azo compounds.

Characterization Of The Electronic Excited-State Energetics And Solution Structure Of Lanthanide(Iii) Complexes With The Polypyridine Ligand 6,6'-Bis[Bis(2-Pyridylmethyl)Aminomethyl]-2,2'-Bipyridine, Gilles Muller, P. Gawryszewska, J. Sokolnicki, A. Dossing, J. P. Riehl, J. Legendziewicz

Gilles Muller

Absorption, emission, and excitation spectra for solid-state and solution of Tb(III), Dy(III), and Gd(III) complexes with the polypyridine ligand 6,6‘-bis[bis(2-pyridylmethyl)-aminomethyl]-2,2‘-bipyridine (C36H34N8) are presented. Measurements of excited-state lifetimes and quantum yields in various solvents at room temperature and 77 K are also reported and used to characterize the excited-state energetics of this system. Special attention is given to the characterization of metal-to-ligand energy transfer efficiency and mechanisms. The measurement of circularly polarized luminescence (CPL) from the solution of the Dy(III) complex following circularly polarized excitation confirms the chiral structure of the complexes under study. No CPL is present in the luminescence …

Reduced Macrophage Apoptosis Is Associated With Accelerated Atherosclerosis In Low-Denstiy Lipoprotein Receptor-Null Mice, Michael Sinensky, J. Liu, D. P. Thweke, Y. R. Su, M. F. Linton, S. Fazio

Michael Sinensky

Objective— The majority of apoptotic cells in atherosclerotic lesions are macrophages. However, the pathogenic role of macrophage apoptosis in the development of atherosclerosis remains unclear. Elevated expression of Bax, one of the pivotal proapoptotic proteins of the Bcl-2 family, has been found in human atherosclerotic plaques. Activation of Bax also occurs in free cholesterol-loaded and oxysterol-treated mouse macrophages. In this study, we examined the effect of Bax deficiency in bone marrow-derived leukocytes on the development of atherosclerosis in low-density lipoprotein receptor-null (LDLR−/−) mice. Methods and Results— Fourteen 8-week-old male LDLR−/− mice were lethally irradiated and reconstituted with either wild-type (WT) …

Two Purified Domains Of Telomerase Reverse Transcriptase Reconstitute Sequence-Specific Interactions With Rna, C. M. O'Connor, Cary K. Lai, Kathleen Collins

Biology Faculty Publications

Telomerase reverse transcriptase (TERT) and telomerase RNA (TER) function together to create a uniquely specialized polymerase. Here we have described for the first time domains of bacterially expressed Tetrahymena TERT that interacted directly with TER in the absence of assembly chaperones. We used quantitative binding assays to define TER sequence requirements for recognition by the high affinity RNA binding domain and an independent N-terminal RNA interaction domain. The TERT RNA binding domain and N-terminal RNA interaction domain had distinct, nonoverlapping requirements for TER sequence and structure that together accounted for all of the sites of TER contact inferred for full-length …

Development Of An Upper Level Undergraduate Research Based Laboratory: The Purification, Analysis, And Dinetic Study Of Cytochrome B5, Mary Mcphail

Senior Honors Theses and Projects

The purpose of this project was to develop an upper level undergraduate biochemistry laboratory (CHEM 453) based upon a novel research project, designed to replace an existing instructional laboratory that employs ‘cookbook’ exercises. Methods for the expression, purification, spectral analysis of structural integrity, and electron transfer capability of rabbit cyt b₅ were adapted from published work done by Dr. Lucy Waskell of the University of Michigan and Dr. Mansuy of the University of Paris. In our hands, rabbit liver cyt b₅ expressed in E. coli was purified to 45% specific content of the theoretical content. Additionally, 37 nmol …

Photocontrol Of Upper And Lower Rim Complexation Of Neutral And Cationic Species By P-Tert-Butylcalix[4]Arene Tetraethyl Ester, Mary Deasy, Bernadette Creaven, Brian A. Murray, Catherine Mckenna, Darren Tobin

Articles

A number of sodium salt complexes of p-tert-butylcalix[4]arene tetraethyl ester, 1, were isolated both with and without upper-rim encapsulated solvent. Selective decomplexation of lower rim bound sodium cations and upper rim encapsulated solvent molecules could be successfully achieved using low pressure light sources. Oxidation of the counter anion at the lower rim of p-tert-butylcalix[4]arene tetraethyl ester triggered both the upper and lower rim decomplexation process. The extent of decomplexation at both rims is controlled both by the nature of the counter-anionic species at the lower rim and by the fate of the photoproducts generated. The calixarene host …

Grouping Www Image Search Results By Novel Inhomogeneous Clustering Method, Gu Xu, Zhiwei Li, Mingjing Li, Wei-Ying Ma, Hong-Jiang Zhang

Mechanical and Aerospace Engineering Faculty Research & Creative Works

In this paper, a novel inhomogeneous clustering method is proposed for grouping web images. It is used to re-organize the search result of web image search engines into a hierarchical structure so that the users can conveniently browse the search result. This method takes into account various features associated with web images, and treats them in different ways. For the surrounding text extracted from the containing web pages, co-clustering approach is adopted; for low-level features of the image content and other features, one-way clustering approach is adopted. The clustering results of different approaches are combined together to produce the final …

The Effect Of Cu-Doping On The Magnetic And Transport Properties Of La₀.₇Sr₀.₃Mno₃, M. S. Kim, Jinbo Yang, Qingsheng Cai, X.-D. Zhou, William B. Yelon, Paul Ernest Parris, William Joseph James

Physics Faculty Research & Creative Works

The effects of Cu-doping on the structural, magnetic, and transport properties of La0.7Sr0.3Mn1xCuxO3 (0<=x<=0.20) have been studied using neutron diffraction, magnetization, and magnetoresistance (MR) measurements. All samples show the rhombohedral structure with the R[overline 3]c space-group from 10 K to room temperature (RT). Neutron diffraction data suggest that some of the Cu ions have a Cu3+ state in these compounds. The substitution of Mn by Cu affects the MnO bond length and Mn-O-Mn bond angle resulting from the minimization of the distortion of the MnO6 octahedron. Resistivity measurements show that a metal to insulator transition occurs for the x>=0.15 samples. The x=0.15 sample shows the highest MR([approximate]80%), which might result from the co-existence of Cu3-Cu2+ and the dilution effect of Cu-doping on the double exchange interaction

Vibrational Dependence Of The H2–H2 C6 Coefficients, Robert Hinde

Chemistry Publications and Other Works

We use the sum-over-states formalism to compute the imaginary-frequency dipole polarizabilities for H₂, as a function of the H–H bond length, at the full configuration interaction level of theory using atom-centered d-aug-cc-pVQZ basis sets. From these polarizabilities, we obtain isotropic and anisotropic C₆ dispersion coefficients for a pair of H₂ molecules as functions of the two molecules’ bond lengths.

Metathesis Key In Production Of Pharmaceuticals, Plastics, Aldemaro Romero Jr., Michael J. Panigot

Publications and Research

No abstract provided.

On-Road Emissions In Asia Measured By Remote Sensing (Presentation), Donald H. Stedman, Gary A. Bishop

Fuel Efficiency Automobile Test Publications

No abstract provided.

Vehicle Remote Sensing For Nitrogen Dioxide (Presentation), Thomas R. Dalton, Gary A. Bishop, Donald H. Stedman

Fuel Efficiency Automobile Test Publications

No abstract provided.

Nature's Assembly Line Logic For Natural Products, Christopher T. Walsh, Ryan G. Kruger, David A. Vosburg

All HMC Faculty Publications and Research

Nature fashions a very large number of diverse products (molecular weights ranging from ca. 200 to 2000 daltons) from simple monomeric metabolites used in primary metabolism. These include polyketide scaffolds generated from the simple C₃ malonyl CoA and C₄ methylmalonyl CoA monomers and nonribosomal peptides made from both the 20 proteinogenic amino acids and dozens of nonpoteinogenic amino acids.¹ A large family of terpenoid skeletons are built from the Δ²- and Δ³-alkene isomers of the biological isoprene monomer, isoprenyl-pyrophosphate.²

A Theoretical Investigation Of Charge Transfer In Several Substituted Acridinium Ions, Jason Lappe '00, Robert J. Cave, Marshall D. Newton, I.V. Rostov

All HMC Faculty Publications and Research

We present calculations for various properties of the ground and excited states of several arylamine-substituted acridinium ion systems that have been studied experimentally. Using ab initio and semiempirical quantum mechanical methods together with the generalized Mulliken−Hush (GMH) model, we examine the excitation energies, dipole moment shifts, and electronic coupling elements for the vertical charge shift (CSh) processes in these systems. We also examine solvent effects on these properties using a dielectric continuum reaction field model. The results are in generally good agreement with available experimental results and indicate that there is strong electronic coupling in these systems over a wide …

Preservation Of Eumelanin Hair Pigmentation In Proopiomelanocortin-Deficient Mice On A Nonagouti (A/A) Genetic Background, Andrzej Slominski, Przemyslaw M. Plonka, Alexander Pisarchik, James L. Smart, Virgine Tolle, Jacobo Wortsman, Malcolm J. Low

Faculty Publications - Department of Biological & Molecular Science

No abstract provided.

Electrochemical Detection Of Nanoscale Phase Separation In Binary Self-Assembled Monolayers, R. Carlisle Chambers, Christina E. Inman, James E. Hutchison

Faculty Publications - Department of Biological & Molecular Science

Developing methods to probe the nature and structure of nanoscale environments continues to be a challenge in nanoscience. We report a cyclic voltammetry investigation of internal, hydrogen-bond driven phase separation of amide-containing thiols and alkane thiols. Amide-containing thiols with a terminal ferrocene carboxylate functional group were investigated in two binary monolayers, one homogeneously mixed and the other phase separated. The electrochemical response of the ferrocene probe was used to monitor adsorbate coverage, environment and phase separation within each of these monolayers. The results demonstrate that the behavior of ferrocene containing monolayers can be used to probe nanoscale organization.

Studies Of Unusual Packing And Of Polymorphism In Two Crystal Systems, Xiang Hao

University of Kentucky Doctoral Dissertations

Crystal structures of anhydrous pinacol, the hexagonal pinacol, pinacol monohydrate, and pinacol hexahydrate were studied. In all the structures crystal packing is unusual and complicated. The origin of the complexity may be the difficulty in filling space densely and while also satisfying the H-bonding requirements when the molecule has few internal degrees of freedom.

Five 15-crown-5 complexes of M(NO₃)₂ (M = Cu, Zn, Mg, Co, Mn) were synthesized and characterized using X-ray diffraction and differential scanning calorimetry. The system is rich in polymorphs. Nine definite solid-state phases were identified. More phases probably exist in the solid state …

Optimization Of An Acrylamides-Based Photopolymer For Reflection Holographic Recording, Raghavendra Jallapuram

Doctoral

Photopolymers have been the subject of special attention in the last two decades. The advantage of being self-developing makes them a practical alternative to silver halide photographic emulsions in holographic interferometry applications. This thesis is aimed at understanding diffusion properties and optimization of an acrylamide-based green sensitized photopolymer material for reflection holographic recording. The composition of the photopolymer includes a green sensitive dye (erythrosine B), acrylamide (monomer), electron donor (triethanolamine) a cross linking monomer (NN’methylenebisacrylamide) and a binder (polyvinyl alcohol). On illumination with light of the appropriate wavelength the dye absorbs a photon and enters into an excited state. The …

A New Approach To The Synthesis Of Pvc Graft Copolymers, Guangde Chen

Dissertations, Theses, and Masters Projects

No abstract provided.

An Hmm-Based Framework For Video Semantic Analysis, Gu Xu, Yu-Fei Ma, Hong-Jiang Zhang, Shiqiang Yang

Chemistry Faculty Research & Creative Works

Video semantic analysis is essential in video indexing and structuring. However, due to the lack of robust and generic algorithms, most of the existing works on semantic analysis are limited to specific domains. In this paper, we present a novel hidden Markove model (HMM)-based framework as a general solution to video semantic analysis. In the proposed framework, semantics in different granularities are mapped to a hierarchical model space, which is composed of detectors and connectors. In this manner, our model decomposes a complex analysis problem into simpler subproblems during the training process and automatically integrates those subproblems for recognition. The …

Heavy Metal Complexes Of Mixed S,N Donor Ligands: X-Ray Crystallography And Solution-State 1h Nmr, Wei Lai

Dissertations, Theses, and Masters Projects

No abstract provided.

In Situ Remediation Of Heavy Metal Contaminated Sediments Using Emulsified Zero-Valent Metal Particles, Kristen Marie Milum

Electronic Theses and Dissertations

Sediments can act as both a sink for pollutants and a source for aquatic contaminants. Natural and human disturbances of the sediments can release the contaminants to the overlying water where bottom dwelling, or benthic, organisms may be exposed through direct contact, ingestion of sediment particles, or uptake of dissolved contaminants present in the water. Dredging, the most common remediation technology for heavy metals, exacerbates this process. The in situ use of emulsified metal has been studied for its ability to pull heavy metals from aqueous solution and from saturated soils. It has proven successful in the laboratory with removal …

The Use And Development Of Laser Microdissection To Separate Spermatozoa From Epithelial Cells For Str Analysis, Christine Sanders

Electronic Theses and Dissertations

Short Tandem Repeat (STR) analysis has become a valuable tool in identifying the source of biological stains, particularly from the investigation of sexual assault crimes. Difficulties in analysis arise primarily in the interpretation of mixed genotypes when cell separation of the sexual assailant's sperm from the victim's cells is incomplete. The forensic community continues to seek improvements in cell separation methods from mixtures for DNA typing. This report describes the use of laser microdissection (LMD) for the separation of pure populations of spermatozoa from two-donor cell mixtures. In this study, cell separation was demonstrated by microscopic identification of histologically stained …