Chemistry Commons^™

(N2o)2⋅So2: Rotational Spectrum And Structure Of The First Van Der Waals Trimer Containing Sulfur Dioxide, Rebecca A. Peebles, Robert L. Kuczkowski

Faculty Research and Creative Activity

No abstract provided.

(N2o)2⋅So2: Rotational Spectrum And Structure Of The First Van Der Waals Trimer Containing Sulfur Dioxide, Rebecca Peebles, Robert Kuczkowski

Faculty Research and Creative Activity

No abstract provided.

On The Vertical And Adiabatic Excitation Energies Of The 21a(G), State Of Trans-1,3-Butadiene, Jason Lappe '00, Robert J. Cave

All HMC Faculty Publications and Research

The excitation energy to the 2¹A_g state of trans-1,3-butadiene is examined using a variety of ab initio electronic structure techniques. While analogous states have been shown to be the lowest singlet excited states for all longer polyenes, for butadiene the position of the 2¹A_g state relative to the HOMO → LUMO excitation (1¹B_u) has been difficult to establish theoretically. We employ a variety of methods (CASSCF, CASPT2, MRSDCI, QDVPT) to examine both the vertical and adiabatic excitation energies for this state. At the ground-state geometry, the vertical excitation energies …

Electronic Properties Of Small Neutral And Charged Beryllium Clusters, Andrew M. Kolchin, Randall W. Hall

Collected Faculty Scholarship

We determine the atomic and electronic structures for neutral and singly positively chargedberyllium clusters containing from two to six atoms using density functional theory in the local spin density approximation. Ions are moved with a steepest descent method and the electronic wave functions optimized using a fictitious dynamics with simulated annealing, as conceived by Car and Parrinello [Phys. Rev. Lett. 55, 2471 (1985)]. Shell-like orbitals, filling angular momentum states in the order: 1s 1p 2s 1d are obtained. We employ a Mulliken population analysis using an atomic basis to examine how the shell orbitals arise from atomic orbitals. This analysis …

Studies Of Tryptophans In Membrane- Spanning "Walp" Peptides By Deuterium Nmr Spectroscopy, Nichole Reed

Inquiry: The University of Arkansas Undergraduate Research Journal

WALP pep tides of sequence acetyl-Gly-Trp-Trp-(Leu-Ala)-Trp-Trp-Ala-ethanolamine insert into lipid bilayers as membrane-spanning a-helices and modulate the lipid phase behavior as functions of n and the lipid acyl chain length. A key feature of the WALP peptides is the positioning of tryptophan (Trp) indole rings at the membrane/water interface. For the examples WALP19 with n = 6.5 and WALP23 with n = 8.5, we have labeled individual indoles with deuterium and incorporated the labeled peptides in oriented, hydrated bilayers of Dimyristoyl-phosphatidylcholine (DMPC). Deuterium NMR spectra from these samples show sharp resonances when the membrane normal is aligned either parallel (Beta = …

Cytotoxic Mab From Rheumatic Carditis Recognizes Heart Valves And Laminin, Jeffrey E. Galvin, Mark E. Hemric, Kent Ward, Madeleine W. Cunningham

Faculty Publications and Presentations

Anti-streptococcal antibodies cross-reactive with N-acetyl-bD-glucosamine (GlcNAc) and myosin are present in the sera of patients with rheumatic fever (RF). However, their role in tissue injury is not clear. In this study, we show that anti-GlcNAc/anti-myosin mAb 3.B6 from a rheumatic carditis patient was cytotoxic for human endothelial cell lines and reacted with human valvular endothelium and underlying basement membrane. Reactivity of mAb 3.B6 with the valve was inhibited by human cardiac myosin > laminin > GlcNAc. The mAb 3.B6 epitopes were localized in fragments of human cardiac myosin, including heavy meromyosin (HMM), the S1 subfragment, and two light meromyosin (LMM) peptides containing …

Magnitudes Of Back Diffusion During Long-Term Diffusive Sampling Of Volatile Organic Compounds Using Carbotrap And Chromosorb 106, Naci̇ye Kiliç, James A. Ballantine

Turkish Journal of Chemistry

The aim of the research was to investigate the magnitudes of the losses of some volatile organic compounds from the solid adsorbents, Carbotrap and Chromosorb 106 due to back diffusion during long-term diffusive sampling of volatile organic compounds in the environment. Experiments were performed by loading the compounds to be tested on the adsorbent tubes and leaving them in an outdoor environment to simulate the real life sampling conditions over a 14 day period. The losses due to back diffusion were investigated for both the high and the low initial concentrations of the fourteen compounds covering a wide range of …

Synthesis Of A New Dihydropyridine Derivative Containing A Known Vasodilator Khellin, Gülgün Ayhan Kilcigi̇l, Meral Tunçbi̇lek, Rahmi̇ye Ertan, Kevser Erol, Engi̇n Yildirim

Turkish Journal of Chemistry

The synthesis and spasmolytic activity of a novel dihydropyridine derivative which contains a vasodilator furanochromone khellin at the 4^{th}$ position of the dihydropyridine ring via the Hantzsch method from khellin-2-carboxaldehyde is described.

Synthetic Metal Alloys: Preparation Of Polyaniline/Polypyrrole Alloys In Protic Medium, Fati̇h Köleli̇, Meltem Düdükcü, Yasemi̇n Arslan

Turkish Journal of Chemistry

Pyrrole and aniline solutions were mixed in different ratios and oxidized under anodic conditions on Pt surface in protic medium. The electrocopolymerization and electrochemical properties of these alloys were investigated. Current-potential diagrams of polyaniline (PA), polypyrrole (PP) and the resulting alloys were recorded and their electrochemical characterizations were identified. In-situ resistance measurements of synthesized alloys were carried out with a home-made apparatus. Conductivity of alloys showed changes depending on applied potential as intrinsic polymers. The electrochemical behaviour of homopolymers and alloys was studied at different temperatures.

X-Ray Powder Diffraction And Ir Study Of Calcium Borophosphate Cabpo_5, A. Baykal, G. Gözel, Meral Kizilyalli, M. Toprak, R. Kniep

Turkish Journal of Chemistry

In this study, CaBPO_5 was synthesized by different solid state reactions than reported before and its X-ray powder diffraction and IR data were reported. In one of these solid state reactions BPO_4 was used as a phosphating agent. The examination of the X-ray powder diffraction data showed that this compound crystallized in a hexagonal system and the refined unit cell parameters were a = 6.684, c = 6.616(2) \AA, with Z=3 as reported before. From the observed reflections, the space group was determined as P3_121, and its density was found to be 3.15 g/cc. The X-ray powder diffraction and IR …

Determination Of Thermal Maturity And Organic Matter Type By Principal Components Analysis Of The Distributions Of Polycyclic Aromatic Compounds, Michael A. Kruge

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

The thermal maturity and organofacies sensitivity of polycyclic aromatic compound (PAC) distributions was explored by examination of the aromatic fractions of solvent extracts from a diverse set of 53 shales, coals and kerogen macerals which have undergone either natural or artificial maturation and which represent all three principal sedimentary organic matter (OM) types. Systematic changes with maturation were observed in the following groups of isomers: tri- and tetramethylnaphthalenes, methyl- and dimethylphenanthrenes, methyl- and dimethyldibenzothiophenes, methylpyrenes, and methylchrysenes. The maturity differences were quantified by mathematical ratios of the relative concentrations of the more thermally stable isomers to the less stable, on …

Solvent As Electron Donor:  Donor/Acceptor Electronic Coupling Is A Dynamical Variable, Edward W. Castner Jr., Darcy Kennedy '00, Robert J. Cave

All HMC Faculty Publications and Research

We combine analysis of measurements by femtosecond optical spectroscopy, computer simulations, and the generalized Mulliken−Hush (GMH) theory in the study of electron-transfer reactions and electron donor−acceptor interactions. Our focus is on ultrafast photoinduced electron-transfer reactions from aromatic amine solvent donors to excited-state acceptors. The experimental results from femtosecond dynamical measurements fall into three categories:  six coumarin acceptors reductively quenched by N,N-dimethylaniline (DMA), eight electron-donating amine solvents reductively quenching coumarin 152 (7-(dimethylamino)-4-(trifluoromethyl)coumarin), and reductive quenching dynamics of two coumarins by DMA as a function of dilution in the nonreactive solvents toluene and chlorobenzene. Applying a combination of molecular …

Hammett Correlations Of The Sulfonamide Proton Chemical Shift In A Series Of N-(Substituted Aryl)-P-Toluenesulfonamides, Frank L. Setliff, Tyson K. Spradlin

Journal of the Arkansas Academy of Science

No abstract provided.

Versatile Apparatus For Measuring Kinetics Of Gaseous Reactions By A Relative Method, Edmond W. Wilson Jr., Holly A. Sawyer, Amber A. Sawyer

Journal of the Arkansas Academy of Science

It is important that accurate, reproducible values for the rates of chemical reactions occurring in the atmosphere be obtained. The value of accurate kinetics measurements is to improve the accuracy of mathematical models used to forecast the state of the atmosphere. We describe a versatile, robust apparatus for obtaining atmospheric reaction rate values and their temperature dependencies by a relative method. This relative method has the advantage over absolute methods in that errors due to impurities and adsorption on walls of the reaction apparatus are minimized. In addition, relative values serve as an important verification for absolute values. The apparatus …

Polybutadiene Cross-Linked With Various Diols – Effect On Thermal Stability, Fawn Marie Uhl, Michael A. Mckinney, Charles A. Wilkie

Chemistry Faculty Research and Publications

The relationship between cross-linking and thermal stability as related to polybutadiene is the focus of current research. Cross-linked polybutadienes have been prepared using various diols as the cross-linking agent. Cross-linked polymers have been characterized by gel content, swelling ratios, infrared spectroscopy, and thermal analysis. These polymers are not highly cross-linked, as seen by gel content and swelling ratios, and cross-linking does not have a large effect on the onset temperature of the degradation. Nonetheless, extensive formation of a non-volatile residue occurs.

Applicability Of Ozone In Small Drinking Water Systems, Craig D. Adams, Justin Sutherland

Civil, Architectural and Environmental Engineering Faculty Research & Creative Works

The use of ozone in water treatment plants is expanding rapidly in the United States. Ozone offers excellent disinfection properties (including chlorine-resistant pathogens) and does not form trihalomethanes. Additionally, ozone can be used to achieve or control many other water quality parameters such as color, taste and odor, and inorganic and organic contaminant concentrations. Control of ozone's disinfection byproducts such as bromate (formed in high bromide waters) is required. This presentation will review the synergistic effects of ozone applicable to use in small water treatment plants.

Dynamics Of Interfacial Polymers In Composites, Frank D. Blum, Wuu-Yung Lin

Chemistry Faculty Research & Creative Works

Much experimental and theoretical work has been done on the behavior of adsorbed polymers. However, not much work has focused on the dynamics, especially segmental dynamics, of the adsorbed polymers. This is especially true of filled polymer or composite systems as the interfacial layers in these systems are difficult to study with most techniques. NMR is not restricted to use in optically clear samples and its use in the characterization in the surface polymers has been reviewed. In our laboratory, we have found that deuterium NMR could be used to probe the segmental dynamics of adsorbed polymers. The position of …

Microhollow Cathode Discharge Excimer Lamps, Karl H. Schoenbach, Ahmed El-Habachi, Mohamed M. Moselhy, Wenhui Shi, Robert H. Stark

Bioelectrics Publications

Microhollow cathode discharges are high-pressure, nonequilibrium gas discharges between a hollow cathode and a planar or hollow anode with electrode dimensions in the 100 μm range. The large concentration of high-energy electrons, in combination with the high-gas density favors excimer formation. Excimer emission was observed in xenon and argon, at wavelengths of 128 and 172 nm, respectively, and in argon fluoride and xenon chloride, at 193 and 308 nm. The radiant emittance of the excimer radiation was found to increase monotonically with pressure. However, due to the decrease in source size with pressure, the efficiency (ratio of excimer radiant power …

A Computational Approach To Determining Stability Constants For Transition Metal Ion Complexes, Jason St. Clair

Honors Theses

The complexation of metal ions in natural waters plays a critical role in defining the metal's biogeochemistry, Numerous investigators have used various experimental techniques to measure complexation constants in the laboratory, but many constants are still poorly undefined or have yet to be investigated due to the difficulty of some of the experiments. A computational approach to obtaining these constants for complexes of Fe(lII), Fe(D), Cr(lli), Cu(lI), Zn(II), and Cd(II) was explored with varying degrees of success. Calculated Gibbs Free Energies were compared to experimental stability constants. Calculations were performed using Spartan's DFT package at the pEP level and with …

Cisplatin Interstrand Cross-Linking Of Defined Sequence Nucleosomal Dna, Erin Elizabeth Wilkes

Honors Theses

DNA interstrand cross-linking agents have been recognized for many years to be powerful antitumor chemotherapeutics. While the interactions between free DNA and many anticancer drugs have been explored extensively, there is less infonnation available about these interactions with nucleosomal DNA. Nitrogen mustards have been reported to exhibit relatively similar cross-linking sites and efficiencies of binding in free and nucleosomal DNA, but mitomycin C exhibits markedly reduced cross-linking near the center of nucleosomal DNA. This current study focuses on cisplatin interstrand cross-linking of the 154 base pair 55 rRNA gene fragment of Xenopus borealis reconstituted with histones from chicken erythrocytes. The …

A Catechol Approach To Natural Product Synthesis, Michelle E. Weber

Honors Theses

This research has focused on the total synthesis of the iron--chelating natural product 1-(2,3-hydroxyphenyl)-4-methoxy-I-butanone. An extract of the iron-cleficient fungus Gleophyllwn lraebeum, this molecule is thought to bind to Fe3+ in a hexacoordinate system to aid in transport through cell walls in order to help regulate iron levels in such iron-deficient fungi. Since the proposed structure of the molecule is based only on the spectral data of a very small sample, our hope is to synthesize and confirm its structure as the extract of the brown rot fungus. We have developed a relatively short retrosynthesis for our work on this …

Interactions Of Ti(Iv) And Sn(Iv) Organometallic Complexes With Double-Stranded Dna, Katherine Macdonald Davies

Honors Theses

In order to understand further the interactions that exist between specific organometallic complexes and DNA, reactions of double-stranded calf-thymus DNA with bis(cyclopentadienyl)titanium dichloride [Cp₂TiC1₂] (TDC), bis(t-butylcyclopentadienyl)titanium dichloride [(C₄H₉Cp)₂TiC1₂] (r-butyl TDC), bis(i-propylcyclopentadienly)titanium dichloride [(C₃H₆Cp)2TiCl₂ a-propyl mc), bis(pentamethylcyclopentadienyl) titanium dichloride [(Cp"₂TiC1₂ (pentarnethyl TDC), triphenyltin chloride (Ph₃SnCl), diphenylrin dichloride (Ph₂SnC1₂) , and triphenyltin acetate (Ph₃SnOAc) were performed. The goal of this research is to establish how the fundamental structure and composition of these compounds determine the effecti veness of their DNA interactions. Each metal compound was incubated with calf thymus DNA at several metal: DNA ratios and reactions were maintained at 37°C at …

Validation Of The Thermochemical Cycle Used In Computing Absolute Gas Phase Acidities And A Molecular-Orbital Study Of Protonated Ammonia-Water Cluster Ions, Jeremiah Aeschleman

Masters Theses

This work is comprised of two separate computational projects, an evaluation of the validity of an assumption made when computing absolute gas phase acidities with a thermochemical cycle and a molecular-orbital study of protonated ammonia-water clusters ions.

Relative gas phase acidities are measured experimentally and then adjusted using Hess' law to align them with an absolute scale. In the Hess' law calculation it is assumed that the electron affinity of A• and the ionization energy of H• are independent of temperature. To test this assumption, absolute enthalpies were computed for the anion (A^-) and the radical (A•) at …

Properties Of Electrodeposited Cadmium Sulfide Films For Photovoltaic Devices With Comparison To Cds Films Prepared By Other Methods, Fi̇gen Kadirgan, Duli Mao, Wenjie Song, Tim Ohno, Brian Mccandless

Turkish Journal of Chemistry

Films of CdS for photovoltaic devices were electrochemically deposited on tin oxide coated glass substrates at different conditions. The films were found to be smooth and uniform with a small grain size. X-ray diffraction measurement and analysis indicated a hexagonal phase rather than the cubic phase. The surface composition of the films was investigated by Auger Spectroscopy. Electrochemical deposition parameters were studied to obtain the optimum conditions for the best CdS films. Our films are compared from the pinhole number and particulate point of view with the films prepared by other methods.

Photochemical Processes And Accumulation Of Solar Energy In Oil Luminophors, A. P. Mamedov, M. I. Rustamov, R. A. Dzhafarova, Ch. K. Salmanova

Turkish Journal of Chemistry

Using the methods of absorption spectroscopy, luminescence and EPR there has been studied the mechanism of solar energy accumulation by high boiling products of oil refining and by luminophors prepared on their basis within wide temperature range (77-550 K). The photochemical processes with participation of all main components of oil products and luminophors have been considered. The mechanisms of accumulation of solar energy of the studied products and luminophors have been considered. The mechanism of accumulation of solar energy of the studied products prior and above their pour points have been found to differ significantly. The light energy accumulation and …

Fundamental Noise Studies In Flame Atomic Magneto-Optic Rotation And Atomic Absorption Spectrometry, Ahmet T. İnce, Richard D. Snook, Jhon B. Dawson

Turkish Journal of Chemistry

A study of inherent noise sources present in a purpose built flame atomic magneto-optic rotation (AMOR) spectrometer system was carried out with a view to identifying their sources. Two different optical configurations were employed, a crossed polariser and a 45° offset polariser configuration. The offset polariser configuration was operated in both an AMOR and atomic absorption (AA) mode for the noise measurements. Two main interference frequencies were found to occur in all the optical measurement modes. An interference flame feature frequency (15.5 Hz -39.0 Hz) which arose from an ``organ-pipe'' effect in the gas flow through the flame cooling sheets. …

Auxiliary Controlled Intramolecular 1,3-Dipolar Cycloaddition Reactions Of Chiral Azomethine Ylides, Özdemi̇r Doğan, Philip P. Garner

Turkish Journal of Chemistry

Intramolecular 1,3-dipolar cycloaddition reactions of chiral azomethine ylides obtained by thermal ring opening of chiral aziridines 7a, b and 8a, b are investigated. Synthesis of these aziridines 7a, b and 8a, b is described.

Synthesis And Reactivity Of Some Mannich Bases. Vi. New Arylamine Mannich Bases Derived From 2-Hydroxy-5-Methylacetophenone, Gheorghe Roman, Diana Nanu, Eugenia Comanita, Bogdan Comanita

Turkish Journal of Chemistry

The amine exchange reaction has been applied for obtaining a new series of arylamine Mannich bases from variously substituted aromatic amines and 3-(dimethylamino)-1-(2'-hydroxy-5'-methylphenyl) propan-1-one. The structures of the newly synthesised Mannich bases have been investigated by IR, ^1H- and ^{13}C-NMR and shown to be in good agreement with the proposed ones.

Studies On The Methylation Of 5-Nitro-Benzimidazoles, Mashooda Hasan, Farzana Shaheen, Uzma Yunus

Turkish Journal of Chemistry

Methylation of 2H, 5-nitro- (1) and 2-ethyl, 5-nitro- (2) benzimidazoles separately with methyl iodide in acetone in the presence of potassium carbonate yielded 2H, 5/6-nitro-(3A and 3B) and 2-ethyl, 5/6-nitro- (4A and 4B) methylbenzimidazoles respectively. Methylation of 1 and 2 in dimethylformamide in place of acetone yielded not only 3A, 3B and 4A, 4B respectively, but in addition 1,3-dimethyl-5-nitro-benzimidazol-2-one (5) was also obtained in each case. The structure of the synthesized compounds was determined with the help of mass and ^1H NMR spectroscopic analysis.

Specific Determination Of Hydrogen Peroxide With A Catalase Biosensor Based On Mercury Thin Film Electrodes, F. Ni̇l Ertaş, Suna Ti̇mur, Erol Akyilmaz, Erhan Di̇nçkaya

Turkish Journal of Chemistry

A biosensor for specific determination of hydrogen peroxide was developed using catalase (EC 1.11.1.6) in combination with a mercury film electrode. Catalase was immobilized with gelatine by means of glutaraldehyde on the electrode surface. The biosensor response was monitored by following the reduction peak of dissolved oxygen at around -0.24 V. The peak current changes upon addition of hydrogen peroxide and gives a linear response in a concentration range of 1-50 x 10^{-6} M within a response time of 3 minutes.