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Analysis Of Organic Nitrates In Artic Outflow, Deanna Elyea-Piper

Masters Theses

The Arctic Outflow Study (AOS) was a project funded by the National Science Foundation to assess the impact of tropospheric ozone concentrations by the measurement of oxidized nitrogen. Measurements of arctic outflow were made to assess the seasonal cycle of compounds in arctic air and the partitioning of NOy during transport to the North Atlantic region. These photochemically active compounds are elevated in the arctic during the winter and spring because of the lack of photochemical processes to destroy them.

Measurements of PAN, Alkyl nitrates, NOy, NO, NO₂, CO, HNO₃, O₃, and particulate nitrate …

Thermal Studies Of Complex Formations Of First Row Transition Metals With Phenolic Compounds In Aqueous Solution, Nabil Adnan Amro

Masters Theses

The coordination chemistry of protocatechuic acid and catechols with the first row of transition metals was studied as a model for the more complicated natural humic substance.

The reaction between Mn²⁺, Fe³⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺ and the phenols, catechol and protocatechuic acid in aqueous solution was studied by the spectrophotometric method. The composition of the complexes formed was determined by continuous variation, iso-molar series and molar ratio methods. The presence of complexes with metal:ligand ratio of 1:1, 1:2 and 1:3 was established in the pH range 3 to …

Molecular Cloning And Functional Analysis Of Polyphosphoinositide-Dependent Phospholipase D, Pldβ, From Arabidopsis, Kirk Pappan, Wensheng Qin, Jim Dyer, Ling Zheng, Xuemin Wang

Department of Chemistry and Biochemistry Faculty Scholarship and Creative Works

A novel plant phospholipase D (PLD; EC 3.1.4.4) activity, which is dependent on phosphatidylinositol 4,5-bisphosphate (PIP2) and nanomolar concentrations of calcium, has been identified in Arabidopsis. This report describes the cloning, expression, and characterization of an Arabidopsis cDNA that encodes this PLD. We have designated names of PLDβ for this PIP2- dependent PLD and PLDα for the previously characterized PIP2-independent PLD that requires millimolar Ca2+ for optimal activity. The PLDβ cDNA contains an open reading frame of 2904 nucleotides coding for a 968-amino acid protein of 108,575 daltons. Expression of this PLDβ cDNA clone in Escherichia coli results in the …

Reactions Of Hydroxylamine With Metal Porphyrins, In Kyu Choi, Yanming Liu, Zhongcheng Wei, Michael D. Ryan

Chemistry Faculty Research and Publications

The reaction of hydroxylamine with a series of metal porphyrins was examined in methanol/chloroform media. The reductive nitrosylation reaction was observed for the manganese and iron porphyrins, leading to a nitrosyl complex that precipitated out of the solution in good isolatable yield (80−90%). This reaction could be used synthetically for the generation of iron and manganese porphyrin nitrosyl complexes and was particularly useful for making isotopically labeled nitrosyl complexes. On the other hand, Co^II(TPP) and Cr(TPP)(Cl) did not react with hydroxylamine under anaerobic conditions. With trace amounts of oxygen, the reaction of Co^II(TPP) with hydroxylamine led …

Quantitation Of Ethidium-Stained Closed Circular Dna In Agarose Gels, Michael F. Shubsda, Jerry Goodisman, James C. Dabrowiak

Chemistry - All Scholarship

The fluorescence of ethidium bromide (EB) bound to equimolar amounts of supercoiled form I and unstrained linear form III pBR322, SV40 and PM2 DNA in agarose gels has been measured by scanning a photographic negative of the gel with a microdensitometer. For SV40 and PM2 DNA, commonly used staining conditions cause both forms, i.e. linear and supercoiled, to fluoresce to the same extent. This obviates the need to use a correction factor for the fluorescence of form I DNA when measuring the amount of this form relative to the amounts of unstrained forms in agarose gels. In the case of …

Monte Carlo Simulation Of The Solid To Superliquid Phase Transition Of Langmuir Monolayers. Ii. Characteristics Of Phase Transition, M.D. Gibson, D.R. Swanson, Craig J. Eckhardt, Xiao Cheng Zeng

Craig J. Eckhardt Publications

The restricted-to-free rotator phase transition of fatty acid monolayers has been modeled using a potential which represents the amphiphiles as planar cross sections of fourfold symmetry. Using much larger system sizes than paper I [D. R. Swanson, R. J. Hardy, and C. J. Eckhardt, J. Chem. Phys. 99, 8194 (1993)], Monte Carlo simulations of the isobaric–isothermal ensemble of model systems with varied number of objects were undertaken to study the effect of system size on the characteristics and order of the phase transition. A peak in the specific heat vs temperature curve was observed near the transition. For each system …

Oxidized Sterols In Patients With Diabetic Heart Disease And Microwave-Mediated Stereoselective Synthesis Of 3-Keto Cholesterol And Cholesterol Epoxide, Cholesteryl Ester Epoxides, Meenakashi N. Kothavale

Theses

Oxidized low density lipoproteins (ox-LDL) may play important role in mediating hypercholesterolemic endothelial dysfunction. The uptake of modified LDL by macrophages to form foam cells has been implicated in the enhancement of atherosclerosis. Recent reports have suggested that when LDL undergoes oxidation in vitro , it is accompanied by a substantial loss of free and esterified cholesterol leading to the formation of oxidation products of cholesterol ( oxysterols). These compounds are present in human atherosclerotic plaques and in human foam cells.

In this regard we have recently studied the plasma sterol composition in diabetic heart patients We have found cholesterol …

Nucleotide Or Nucleoside Photoaffinity Compound Modified Antibodies, Methods For Their Manufacture And Use Thereof As Diagnostics And Therapeutics, Boyd E. Haley, Heinz Köhler, Krishnan Rajagopalan, Gabriela Pavlinkova

Chemistry Faculty Patents

Sites on antibodies having affinity for photoaffinity compounds, in particular purine or azidopurine containing compounds are taught. These sites provide for the site-specific attachment of nucleotide photoaffinity compounds to antibodies, e.g., ATP- or GTP-analog photoaffinity compounds by photochemical reaction. These nucleotide photoaffinity compounds may additionally be attached to molecules having a desired therapeutic or diagnostic activity, and the resultant conjugates used as diagnostics or therapeutics.

Synthetic Strategies For The Construction Of Enantiomeric Azanoradamantanes, Daniel Becker, Roger Nosal, Daniel L. Zabrowski, Daniel Flynn

Chemistry: Faculty Publications and Other Works

The amino azanoradamantane hexahydro-2,5b-methano-IH-3aS,3aa,6aa-cyclopenta-[clpyrrole-4a-amine 1and the corresponding enantiomer ent-1 have been prepared along with benzamide derivatives SC-52491and SC-52490, respectively, which are of pharmaceutical interest. The key meso-azabicyclo[3.3.0] intermediate 3 was prepared via three separate routes: a [3+2] cycloaddition route, a radical cyclization/ionic cyclization route, and a reductive Pauson-Khand route.

Identification Of The Adp-L-Glycero-D-Manno-Heptose-6-Epimerase (Rfad) And Heptosyltransferase Ii (Rfaf) Biosynthesis Genes From Nontypeable Haemophilus Influenzae 2019, W A. Nichols, B W. Gibson, William Melaugh, N G. Lee, M Sunshine, M A. Apicella

Chemistry Faculty Publications

Haemophilus influenzae is an important human pathogen. The lipooligosaccharide (LOS) of H. influenzae has been implicated as a virulence determinant. To better understand the assembly of LOS in nontypeable H. influenzae (NtHi), we have cloned and characterized the rfaD and rfaF genes of NtHi 2019, which encode the ADP-L-glycero-D-manno-heptose-6-epimerase and heptosyltransferase II enzymes, respectively. This cloning was accomplished by the complementation of Salmonella typhimurium lipopolysaccharide (LPS) biosynthesis gene mutants. These deep rough mutants are novobiocin susceptible until complemented with the appropriate gene. In this manner, we are able to use novobiocin resistance to select for specific NtHi LOS inner core …

Characterization Of A Transposon Tn916-Generated Mutant Of Haemophilus Ducreyi 35000 Defective In Lipooligosaccharide Biosynthesis, B W. Gibson, A A. Campagnari, William Melaugh, M A. Apicella, S Grass, Jing Wang, Katherine L. Palmer, R S. Munson

Chemistry Faculty Publications

To define the role of the surface lipooligosaccharide (LOS) of Haemophilus ducreyi in the pathogenesis of chancroid, Tn916 mutants of H. ducreyi 35000 defective in expression of the murine monoclonal antibody (MAb) 3F11 epitope on H. ducreyi LOS were identified by immunologic screening. One mutant, designated 1381, has an LOS which lacks the MAb 3F11 epitope and migrates with an increased mobility on sodium dodecyl sulfate-polyacrylamide gel electrophoresis. The gene disrupted by the Tn916 element in strain 1381 was identified by cloning the sequences flanking the Tn916 element. The sequences were then used to probe a lambda DASHII genomic library. …

Determination Of Selected Hydrocarbon Concentrations In Reformate Using Near Infrared Spectroscopy, Roy Roger Bledsoe Jr.

Theses, Dissertations and Capstones

Near infrared spectroscopy was used as a quantitative technique employing multiple linear regression and partial least squares regression for determining the concentration of hydrocarbon groups and individual hydrocarbons present in reformate, a refinery process stream. Models were generated for total aromatics, benzene, toluene, total xylenes and individual xylene isomers, ethylbenzene, total paraffins, n-hexane, n-heptane, total isoparaffins, isopentane, 2-methylhexane, total naphthenes, methylcyclopentane, and total olefins. Some models are being used with an on-line instrument to constantly monitor a reformate stream as it leaves the reforming unit, with a standard error of performance of 0.118 volume percent for the prediction …

Directed Panspermia. 3. Strategies And Motivations For Seeding Star-Forming Clouds, Michael Noah Mautner

Chemistry Publications

Microbial swarms aimed at star-forming regions of interstellar clouds can seed stellar associations of 10 - 100 young planetary systems. Swarms of millimeter size, milligram packets can be launched by 35 cm solar sails at 5E-4 c, to penetrate interstellar clouds. Selective capture in high-density planetary accretion zones of densities > 1E-17 kg m-3 is achieved by viscous drag. Strategies are evaluated to seed dense cloud cores, or individual protostellar condensations, accretion disks or young planets therein. Targeting the Ophiuchus cloud is described as a model system. The biological content, dispersed in 30 μm, 1E-10 kg capsules of 1E6 freeze-dried microorganisms …

Complexes Between Nascent Polypeptides And Their Molecular Chaperones In The Cytosol Of Mammalian Cells, Daryl K. Eggers, W. J. Welch, W. J. Hansen

Faculty Publications, Chemistry

Folding of newly synthesized proteins in vivo is believed to be facilitated by the cooperative interaction of a defined group of proteins known as molecular chaperones. We investigated the direct interaction of chaperones with nascent polypeptides in the cytosol of mammalian cells by multiple methods. A new approach using a polyclonal antibody to puromycin allowed us to tag and capture a population of truncated nascent polypeptides with no bias as to the identity of the bound chaperones. In addition, antibodies that recognize the cytosolic chaperones hsp70, CCT (TRiC), hsp40, p48 (Hip), and hsp90 were compared on the basis of their …

Sodium Nitrite Alone Protects The Brain O _I_ Microsomal Ca -Atpase Against Potassium Cyanide-Induced Neurotoxicity In Rats, Odutayo O. Odunuge, G.. A. Adenuga

Faculty Publications

The effect of a short-term oral administration of potassium cyanide (KCN) (200 ppm in diet) with or without sodium nitrite (NaNO2) pretreatment on rat brain microsomal Ca2* ATPase was investigated. The specific activity value of the enzyme significantly decreased (p<0.05) by 50% compared with control and by 63% for KCN-treated rats compared with KCN-treated rats pretreated with NaNO;,. There was no significant difference at the h = 0.05 level between the values obtained for the control and KCN-treated rats pretreated with NaNO,. These results show both that feeding lowers brain microsomal Ca2f-ATPase activity and that NaNO, has a protective role (antidote function) in that respect.

Molecular Engineering Of Side-Chain Liquid Crystalline Polymers By Living Polymerizations, Coleen Pugh, Alan L. Kiste

Chemistry and Biochemistry

“Living” anionic, cationic, metalloporphyrin and ring-opening metathesis polymerizations have been used to prepare well-defined side-chain liquid crystalline homopolymers, block and graft copolymers and statistical copolymers. This paper analyzes their successes and failures by reviewing the mechanistic aspects and experimental conditions of each type of polymerization, and identifies other classes of mesogenic monomers that could be polymerized in a controlled manner in the future. The emerging structure/property relationships are then identified using well-defined SCLCPs in which only one structural feature is varied while all others remain constant.

The thermal transitions of liquid crystalline polymethacrylates, polynorbomenes and poly(viny1 ether)s reach their limiting …

Infrared Spectroscopy Of Nickel And Iron Geoporphyrins, Kewei Xu

Theses, Dissertations and Capstones

The first assignments of a number of vibrational modes to the infrared spectra of nickel and iron porphyrins are presented. The purpose of this work was to establish a library of reference spectra which can be used in the identification of geoporphyrins from coal. The infrared regions of 1700-1200 cm·' and 1200-600 cm·1 are informative and display a rich array of skeletal and alkyl substituent modes. The detailed analyses indicate that nickel and iron complexes of the four etioporphyrin (Etio) I-IV isomers exhibit notable differences at certain positions, especially in the 800-700 cm·' and 1000-900 cm·' subregions, which should enable …

The Computational Study Of "Model" Pollutants In Clay Montmorillonite, Sung-Ho Park

Dissertations

No abstract provided.

Immunologic And Hematopoietic Effects Of Cd40 Stimulation After Syngeneic Bone Marrow Transplantation In Mice, Satoshi Funakoshi, Dennis D. Taub, Miriam R. Anver, Arati Raziuddin, Osamu Asai, Prakash Reddy, Helen C. Rager, William C. Fanslow, Dan L. Longo, William J. Murphy

Chemistry Faculty Research & Creative Works

CD40 is a molecule present on multiple cell types including B lymphocyte lineage cells. CD40 has been shown to play an important role in B cell differentiation and activation in vitro, although little is known concerning the effects of CD40 stimulation in vivo. We therefore examined the effects of CD40 stimulation in mice using a syngeneic bone marrow transplantation (BMT) model in an effort to augment B cell recovery after high dose therapy with hematopoietic reconstitution. After the BMT, mice were treated with or without 2-6 μg of a soluble recombinant murine CD40 ligand (srmCD40L) given intraperitoneally twice a week. …

Separation And Artificial Maturation Of Macerals From Type Ii Kerogen, Michael A. Kruge, Patrick Landais, David F. Bensley, B Artur Stankiewicz, Marcel Elie, Olivier Ruau

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

Immature Type II kerogen (HI= 660 mg/g) from the Lower Toarcian of the Paris Basin was separated into an alginite concentrate (HI = 952 mg/g) and an amorphous organic matter (AOM) concentrate (HI = 573 mg/g) by density centrifugation. The flash pyrolyzate of the alginite is characterized by high relative concentrations of several series of n-alkanones and n-alkenones (including mid-chain alkyl ketones), in addition to n-alkanes, n-alk-1-enes and n-alkadienes. To our knowledge, this Toarcian alginite is the oldest example of marine organic matter whose pyrolyzate contains mid-chain alkanones in such high relative concentrations. In sharp …

An Expeditious Synthesis Of Β,Γ-Unsaturated Δ-Lactones: Useful Pharmacological Synthetic Intermediates, Li Xiong

Masters Theses

Two-carbon ring expansions of vinyl β-lactones, were carried out by Lewis acids (BF₃-Et₂O or Et₂AlCl) via an ionization/cation rearrangement. β,γ-unsaturated δ-lactones were produced as efficient protocols for the synthesis of bioactive substances.

Vinyl β-lactones were prepared via ring closure of corresponding unsaturated β-hydroxy acids. Differently structured substrates were examined to study the influence of the substituents on the rearrangement. Other factors, such as temperature, solvent and catalyst were also studied in search of suitable reaction conditions.

This method is moderately successful in providing fused-ring δ-lactones, but higher yields (so far total yield of 24.8%) …

Analytical Applications Of Organic Conducting Polymer Electrodes, Nada F. Atta, George C. Russell, Z. Wang, N. Akmal, J.F. Rubinson, S.K. Lunsford, E. Karagözler, O. Y. Ataman, H. Zimmer, H.B. (Jr.) Mark, Ahmed Galal

Turkish Journal of Chemistry

Electrodes modified by he electrodeposition of conducting polymers were used for the detection and quantitative determination of some inorganic, organic, and biological molecules. Monomers used were five membered ring heterocycles or crown ethers and their derivatives. The polymer films were deposited on glassy carbon or platinum substrates. The resulting electrodes were used in the amperometric mode or in the potentiometric mode for flow injection and chromatographic analyses. The results showed that the proposed modified surface catalyzes the oxidation of organic and biological compounds. The detection of electroinactive inorganic anions, such as F^-, Cl^-, Br^-, NO_2^- and NO^-_3 was also possible …

Synthesis Of An Organophosphorus Analog Of Acetylcholine, Darshan Mehta '97

Honors Projects

Acetylcholinesterase (AChE) is an important enzyme in our nervous system In normal nerve function, AChE catalyzes the hydrolysis of acetylcholine (ACh) into its respective components, choline and acetate. Recent interest has been focused on AChE because of its potential role in the pathology of neurodegenerative diseases such as Alzheimer's disease. Studies have revealed that the active site of AChE contains an esteratic and several hydrophobic/anionic subsites. AChE is inhibited by organophosphorus (OP) compounds like sarin and soman. As a result, OP compounds have been used to study the structure of AChE and the mechanism by which it catalyzes the hydrolysis …

Varietal Differences In The Total And Enantiomeric Composition Of Theanine In Tea, K. Helen Ekborg-Ott, Andre Taylor, Daniel W. Armstrong

Chemistry Faculty Research & Creative Works

Theanine is the main amino acid component in tea. It usually constitutes between 1 and 2% of the dry weight of the tea leaves. It is as prevalent in tea as all other free amino acids combined. Both enantiomers of theanine were found to have a similar sweet taste, with little or no aftertaste. It was found that black and half-green teas (except for Formosa Oolong) contained as much, or more, theanine as green teas. No correlation was found between the absolute concentration of theanine in tea and its enantiomeric composition. An inverse correlation was found between certain grades of …

Acidity Studies Of Deuterated Acids And Bases Commonly Used As Buffers In Nmr Studies, Rose M. Mcconnell, Walter E. Godwin, Brant Stanley, M. Shane Green

Journal of the Arkansas Academy of Science

Structure based drug development is currently considered to be an important strategy for drug discovery. This strategy requires that critical knowledge of the three dimensional binding site on receptor molecules be known. NMR studies are frequently employed to ascertain important structural data on individual proteins as well as complexes of proteins with ligands. Deuterium labeled acids and bases are frequently used as buffers in deuterium oxide solutions for NMR studies on the structural conformations of bioactive molecules. Since pH is an important factor in any study of the conformational and stereochemical aspects of biologically active molecules, deuterated buffers are an …

Artificial Neural Networks Used To Predict Electrical Properties Of Polymers, Sanjay K. Mitra, Qing Luo, Jerry A. Darsey

Journal of the Arkansas Academy of Science

The ability to predict properties of molecules prior to their synthesis can be of great importance in optimizing their design. Substantial savings in time as well as cost can be achieved if some desired properties can be predicted prior to the synthesis of the molecule. The outer orbitals of a molecule are primarily responsible for many different properties of the molecules. These outer orbital parameters can be utilized by an intelligent computing system like an Artificial Neural Network to extract necessary knowledge about the properties of the molecule. An Artificial Neural Network was trained to extract electrical parameters of several …

Efficient And General Synthesis Of Novel Β-Polyfluoroalkoxy Vinamidinium Salts, Koichiro Kase, Mitsuyoshi Katayama, Takashi Ishihara, Hiroki Yamanaka, John T. Gupton

Chemistry Faculty Publications

Novel β-polyfluoroalkoxy vinamidinium salts 3 and/or 4 were synthesized in good yields by the reaction of N-(2- polyfluoroalkoxy-3 ,3-difluoro-1-propenyI)trimethylammonium iodides (2), prepared from N-(2,3,3-trifluoro-1-propenyl)trimethylammonium iodide (1), with secondary amines in MeCN at 70 °C for 1 h. The salts were also obtainable in comparable yields by the one-pot reaction of 1 with sodium polyfluoroalkoxide followed by treatment with amines.

Suprachiasmatic Nucleus Neurons Are Glucose Sensitive, Adam C. Hall, Roselle M. Hoffmaster, Edra L. Stern, Mary E. Harrington, David Bickar

Chemistry: Faculty Publications

The suprachiasmatic nucleus (SCN) in the hypothalamus serves as the pacemaker for mammalian circadian rhythms. In a hamster brain slice preparation, the authors were able to record spontaneous activity from SCN cells for up to 4 days in vitro and verify a self-sustained rhythm in firing. The phase of this rhythm was altered by the concentration of glucose in the bathing medium, with time of peak firing advanced for a 20 mM glucose condition and slightly delayed for a 5 mM glucose condition, relative to 10 mM. The advancing effect of 20 mM glucose and the delaying effect of 5 …

Calcium Metabolismn In Volvox Carteri, Bridget Anne Neville

Honors Theses

Calcium metabolism is involved in many ways in the cellular activities of the colonial green alga, Volvox carteri. Various drugs that are known in other systems to cause specific changes in calcium metabolism, gave rise to various visible metabolic effects in this study. These effects provide evidence for calcium's role in Volvox growth and development and in its cytoskeleton. Another way that calcium exerts its effect on Volvox is by acting as a second messenger in a G-protein/inositol phosphate signal transduction pathway.

This study also supports the fact that cytoskeletal components are important for development in Volvox. Both microtubules and …

Computational Studies Of Hydroboration: Remote Functional Groups And Ring Size Effects, Sarah Liberty Olbrich

Honors Theses

This study is a preliminary computational study of the energies of complex molecules. We are looking at the roles of remote heteroatoms in the hydroboration of propellane systems and ring size effects in the solvolysis of cyclic alkyl halides was examined using computational methods. Geometry and transition state optimizations were done using semi empirical (MNDO. AMI) and ab initio (STO-3G, 3-2IG, and 6-31G*) methods. Attempts to correlate computational results with previously reported data will be presented.