Physical Sciences and Mathematics Commons^™

Proton–Donor Properties Of Water And Ammonia In Van Der Waals Complexes With Rare‐Gas Atoms. Kr–H2o And Kr–Nh3, G. Chalasinski, M. M. Szczesniak, Steve Scheiner

Chemistry and Biochemistry Faculty Publications

The perturbation theory of intermolecular forces in conjunction with the supermolecular Møller–Plesset perturbation theory is applied to the analysis of the potential‐energy surfaces of Kr–H₂O and Kr–NH₃ complexes. The valleylike minimum region on the potential‐energy surface of Kr–H₂O ranges from the coplanar geometry with the C₂ axis of H₂O nearly perpendicular to the O–Kr axis (T structure) to the H‐bond structure in which Kr faces the H atom of H₂O. Compared to the previously studied Ar–H₂O [J. Chem. Phys. 94, 2807 (1991)] the minimum has more …

Proton–Donor Properties Of Water And Ammonia In Van Der Waals Complexes With Rare‐Gas Atoms. Kr–H2o And Kr–Nh3, G. Chalasinski, M. M. Szczesniak, Steve Scheiner

Steve Scheiner

The perturbation theory of intermolecular forces in conjunction with the supermolecular Møller–Plesset perturbation theory is applied to the analysis of the potential‐energy surfaces of Kr–H₂O and Kr–NH₃ complexes. The valleylike minimum region on the potential‐energy surface of Kr–H₂O ranges from the coplanar geometry with the C₂ axis of H₂O nearly perpendicular to the O–Kr axis (T structure) to the H‐bond structure in which Kr faces the H atom of H₂O. Compared to the previously studied Ar–H₂O [J. Chem. Phys. 94, 2807 (1991)] the minimum has more …

Calculation Of Barriers To Proton Transfer Using Variations Of Multi-Configuration Self‐Consistent Field Methods. I. Combinations Of Orbitals, K. Luth, Steve Scheiner

Steve Scheiner

The usefulness of multiconfiguration self‐consistent‐field (MCSCF) calculations in computing correlated proton transfer potentials is investigated for the systems HF₂⁻, H₇N₂⁺, H₃O₂⁻, and H₅O₂⁺. In deciding whether to include particular molecular orbitals, it is important to consider the balance of electron density between the donor and acceptor groups and the interactions that are incorporated in the orbitals. Only orbitals which have the proper symmetry to interact with the transferring hydrogen need be included in the MCSCF active space. Reasonable transfer barriers are obtained …

Pulsed‐Laser Excited Differential Photothermal Deflection Spectrometry, Stephen E. Bialkowski, Xu Gu, Pete E. Poston, Linda S. Powers

Stephen E. Bialkowski

This paper describes a differential photothermal optical absorbance apparatus that uses two excitation beams at different wave-lengths. A single probe beam monitors the difference in heats generated by the two wavelengths. The theory is developed for the operational principles of the apparatus, and theoretical signals are compared with those obtained with a conventional absorption spectrophotometer. The differential photothermal apparatus has a theoretical advantage over conventional spectrophotometry for samples with less than unit absorbance. Experiments are described which verify the operating principles and demonstrate the flexibility of the apparatus.

The Synthesis Of Chiral Building Blocks Using Beta-Hydroxy Sulfoxide Dianions, Carla M. Edwards

Master's Theses

No abstract provided.

Syntheses Of Azure-B Neuropeptide Conjugates And A Novel Bicyclic Triene, Milind D. Choubal

Dissertations

No abstract provided.

Intelligent Processing Of Pmr-15, Sean Michael Hart

Dissertations, Theses, and Masters Projects

No abstract provided.

Remote Dianions In The Synthesis Of Indolizidine Alkaloids, Diana L. C. Green Green

Dissertations

No abstract provided.

Resonance Raman Spectra Of Chloroperoxidase Reaction Intermediates, Ann Marie G. Sullivan

Theses and Dissertations

Chloroperoxidase is an enzyme that exhibits spectroscopic and structural properties similar to cytochrome P-450. Chloroperoxidase is studied using resonance Raman spectroscopy to characterize the reaction intermediates of the physiological mechanism, known as compounds I and II. Compound I is formed by a two electron oxidation of the resting enzyme and contains an Fe(IV) porphyrin ℼ cation radical. A one electron reduction of compound I produces the compound II intermediate which contains an oxy-ferryl [Fe(IV)=O] iron heme.

Chloroperoxidase is a heme enzyme of substantial interest because of its structural similarity to cytochrome P-450 and because of its diverse reactivity. Chloroperoxidase can …

Characterizations Of Antimony Tri‐Sulfide Chemically Deposited With Silicotungstic Acid, O. Savadogo, K. C. Mandal

Faculty Publications

No abstract provided.

Melbourne Automobile Emissions Study, Donald H. Stedman, Yi Zhang

Fuel Efficiency Automobile Test Publications

No abstract provided.

Calculation Of Barriers To Proton Transfer Using Multiconfiguration Self‐Consistent‐Field Methods. I. Effects Of Localization, K. Luth, Steve Scheiner

Chemistry and Biochemistry Faculty Publications

The usefulness of multiconfiguration self‐consistent‐field (MCSCF) calculations in computing correlated proton transfer potentials is investigated for the systems HF₂⁻, H₇N₂⁺, H₃O₂⁻, and H₅O₂⁺. In deciding whether to include particular molecular orbitals, it is important to consider the balance of electron density between the donor and acceptor groups and the interactions that are incorporated in the orbitals. Only orbitals which have the proper symmetry to interact with the transferring hydrogen need be included in the MCSCF active space. Reasonable transfer barriers are obtained …

How Arsenic Residues Get In Wool, Tony Martin, Robin Jacob, Marion Davies, Peter Rutherford

Journal of the Department of Agriculture, Western Australia, Series 4

Wool can become contaminated with arsenic in various ways, and several different sources may each contribute to any individual arsenic residue problem.

• dipping sheep in an arsenical dip ( now illegal),

• dipping sheep in a non-arsenical dip in a contaminated dipping facility

• penning sheep on soil with high levels of arsenic before shearing.

Other possible sources include running sheep on land contaminated by gold mine tailings or exploration sites, and allowing sheep access to sites on the farm where arsenical compounds have been dumped, for example, rubbish dumps or sites where dip/sump sludge has been dumped.

Farmers …

A Helium Discharge Detector For The Determination Of Organosulfur And Phosphorus Compounds, Tamara L. Tieman

Dissertations, Theses, and Masters Projects

No abstract provided.

The Imidization Reactions Of Pmr-15 Polyimide, Kerri Ann Robillard

Dissertations, Theses, and Masters Projects

No abstract provided.

Synthesis And Inclusion Of 1-(5-Cyanonaphthyl) Diazomethane With B-Cyclodextrin, Scott Tobias Forrest

Dissertations, Theses, and Masters Projects

No abstract provided.

Characterization Of Polycyclic Aromatic Hydrocarbons (Pahs) By The Kinetics Of Depuration In Bivalve Molluscs, Mercenaria Mercenaria, C Sato, H Kim, John T. Tanacredi Ph.D.

Faculty Works: CERCOM (1977-2016)

The objectives of this study were to examine depuration aspects of polycyclic aromatic hydrocarbons (PAHs) in a hard-shell clam Mercenaria mercenaria, and to characterize PAHs by the depuration kinetics. In this investigation, clams were exposed to artificial sea water containing a mixture of eight PAHs (i.e., naphthalene, fluorene, phenanthrene, flouranthene, pyrene, benz[a]anthracene, chrysene, benzo[a]pyrene) for 48 hours. The clams were then transferred into clean (PAH-free) artificial seawater for release, and sampled at predetermined intervals. The target PAHs were extracted from the clam tissue and quantified by a gas chromatograph equipped with a capillary glass column and FID.

The results …

Ua66/7/3 Coal & Fuel Laboratory 1990-1992 Report, Wku Chemistry

WKU Administration Documents

Report regarding work done at the WKU Coal & Fuel Laboratory between 1990 and 1992.

Butenolide Synthesis Via Cation-Initiated Ring Expansion/Elimination Of Β-Lactones, Jianhua Huang

Masters Theses

An area of recent research in the Black research group is an exploration of the potential of cation-initiated β-lactone ring expansions, accompanied by the elimination of a proton or other electrofuge, as a protocol for the synthesis of multisubstituted butenolides.

Γ-Bromo β-lactones were prepared via bromolactonization of the appropriate β,Γ-unsaturated acids under basic conditions. The nucleofugal bromine atom on the Γ-carbon was then employed to effect carbocation formation adjacent to the lactone ring oxygen atom; the most efficacious reagent combination was found to be silver nitrate in refluxing acetic acid. Generation of this cation initiated a migration of the β-lactone …

Iron Tricarbonyl Derivatives Of Ditertiary Phosphines, Xi Chen

Masters Theses

In this work we have explored reactions of coordinated diphenylvinylphosphine with coordinated diphenylphosphine. Starting materials, (OC)₄FePPh₂CH=CH₂, trans- (OC)₃Fe(PPh₂CH=CH₂)₂, (OC)₄FePPh₂H, and trans- (OC)₃Fe(PPh₂H)₂ were successfully prepared from known procedures. The bimetallic complex, (OC)₄FePPh₂CH₂CH₂PPh₂Fe(CO)₄, was obtained in 69% yield from the reaction of ((OC)₄FePPh₂CH=CH₂ with (OC)₄FePPh₂H. The trimetallic complex, (OC)₄FePPh₂CH₂CH_{2 …}

Studies On Improving The Regioselectivity Of Reactions Of Sucrose: The Role Of Molecular Recognition And Polymer Supported Syntheses, Ran Jiang

Masters Theses

The world economy is critically dependent upon natural resources. Because sucrose can be inexpensively produced in large quantities and refined to a purity unequalled by almost all other natural products, it has been exploited as an industrial raw material for many years, primarily as a sweetener. A major difficulty in utilizing sucrose as an industrial feedstock is the lack of regioselectivity in synthetic reactions due to its eight hydroxyl groups of similar reactivity.

The long range goal in this work is to apply the technique of molecular recognition by template imprinting to the creation of a material that will bind …

New Reagents And Reactions For Desulfurization Of Coal, Shan Wang

Masters Theses

Searching for new reagents and reactions for pre-combustion desulfurization of coal was the goal of this work. In this study, modifications of mild desulfurization reactions, which were found to work with organosulfur model compounds, have been investigated systemetically for improvements in sulfur removal and reduction of reagent cost. The screening of reagents and new reactions utilized substituted thiophenes plus aryl sulfides as the initial models for organosulfur compounds in coal. Tetrahydrofuran extracts of Illinois Basin Coals were also used as second generation targets for desulfurization reactions.

Dibenzothiophene was converted to biphenyl using potassium metal/tetrahydrofuran without the addition of electron transfer …

Model For The Co Poisoning Of Hydrodesulfurization Catalysts. Synthesis And Structure Of {Ru(Co)[Pph2sc12h7)]2cl2}.2ch2br2, Mark Draganjac, Thomas B. Rauchfuss, Arnold L. Rheingold

Journal of the Arkansas Academy of Science

The treatment of {Ru[(PPh2SC12H7)]2Cl2} with CO at ambient conditions results, after work up, in the isolation of the monocarbonylated species {Ru(CO)[(PPh2SC12H7)]2Cl2}, I. Crystals of I(C51H38Br4Cl20P2RuS2; F.W. = 1284.6) are triclinic; Ppa= 11.587(3), b = 13.010(4), c = 17.309(4) A, a = 93.32(2)°, p = 106.51(2)°, y = 91.29(2)°; Z= 2; V=2495(1) A';d^,. = 1.709 gem 1 X(MoKa) = 0.71073 A, = 37.7 cm 1 ;R =0.0748; Rw = 0.0714 for 4141 unique reflections. The geometry about the Ru(II) center is pseudooctahedral, with the phosphine ligands in the trans configuration. The Ru-S bond distance is 2.425(3) A.

4-Substituted Anilides Of 2,6- And 5,6- Dichlorolicotinic Acid. Potential Agricultural Agents, Frank L. Setliff, Nikhil G. Soman

Journal of the Arkansas Academy of Science

A series of 4-substituted anilides of 2,6- and 5,6 dichloronicotinic acid were prepared. The acids were first converted to their acid chlorides, which were in turn treated with the appropriate 4-substituted aniline in chloroform. A total of 16 anilides was thus prepared, and their structures confirmed. These compounds were prepared for testing as possible herbicidal, pesticidal or fungicidal agents

Hammett Correlations In The 1H Nmr Spectra Of Some N-Arlydihalonicotinamides, Frank L. Setliff, Nikhil G. Soman, Jody Z. Caldwell, Debra L. Rogers

Journal of the Arkansas Academy of Science

Excellent linear correlations of amide proton chemical shifts (Snh) (in DMSO-d6 ) with Hammett substituent constants (5) for a series of 4-substituted anilides of four dihalonicotinic acid systems were observed. Dihalonicotinanilides with chlorine in the pyridine 2 - position exhibited a more positive slope in a Hammett plot of S^H vs - aR- where R is the substituent in the 4 position of the benzene ring. This observation is explained in terms of the inductive effect of chlorine which results in a slightly more acidic amide proton, which in turn causes an enhanced hydrogen bonding tendency to solvent. Four disubstituted …

Scf-Mo And Monte Carlo Calculations Of Poly (Dimethylsiloxane), Shannon H. Brownfield, Jerry A. Darsey

Journal of the Arkansas Academy of Science

Self-consistent-field molecular orbital calculations are being used more and more extensively in determining the energies and properties of various confirmations of polymers. We are using the semi-quantum mechanical procedure MNDO (moderate neglect of differential overlap) to obtain various rotational conformations states of poly(dimethylsiloxane) (PDMS). Before calculation of these states, the molecule is geometrically optimized by using the ab initio procedure Guassian 86 at the 3-21G basis set level. Generations of 144 rotational states by rotating about two bonds simultaneously in increments of 30° were created. A potential energy surface was created from which Monte Carlo generated several polymer characteristics including …

Preparation Of Electron Donor And Acceptor Molecules For Porphyrin Derivatization, Christoph Hoefler

Dissertations and Theses

Porphyrins derivatized with electron donating and electron withdrawing groups can be used for artificial photosynthesis. Four new compounds, two electron donors and two electron acceptors, have been synthesized for prospective porphyrin linkages.

Theoretical And Experimental Evaluation Of Hysteresis In Atmospheric Chemistry, Theodore Alan Haigh

Dissertations and Theses

This treatise is a recapitulation of the theoretical and experimental study of hysteresis in atmospheric kinetics. The original problem arose from a theoretical study of a series of reactions for clean air. Upon evaluation a bistable equilibrium was predicted. The steady-state analysis had delineated a metastable region for the set of reactions. This bounded region is the hysteresis that this research project evaluated.

A High Yield Microscale Enzymatic Synthesis And Purification Of 14c‐Labeled Nicotinamide Adenine Dinucleotide Phosphate (Nadp+), Andre Ronneberg, Gordon Metz, Richard Weld, Peter Roffey, Chris Craney

Chris L. Craney

Uniformly labeled (U) 14C nicotinamide adenine dinucleotide phosphate (NADP+) was synthesized by phosphorylating [U-14C]nicotinamide adenine dinucleotide (NAD+) in the presence of immobilized NAD+ kinase. The 15 μCi (600 μL) synthesis consistently achieved yields between 80% and radiochemical purities greater than 95%. The [U-14C]NADP+ was purified by high performance anion-exchange chromatography using a gradient elution of ammonium bicarbonate. This procedure may be applicable to the synthesis of other charged, UV-absorbing products of enzyme-catalyzed reactions.

Experiments In Aerobic And Anaerobic Biodegradation Of Trichloroethylene, Qiong Liao

Theses

The removal of trichloroethylene (TCE) from industrial waste has been intensively studied in recent years, Biodegradation has been determined to be an effective treatment for TCE in the environment. Many researchers have studied the biodegradation of TOE and obtained successful results based on the use of specific isolated bacteria. At the NJIT Biotechnology Laboratory, a new method is being developed in which immobilized activated sludge is used to degrade several toxic chemicals in various reactor configurations. The objective of this research is to determine if these methods can be extended to treat TCE.

Activated sludge from a wastewater treatment plant …