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Selective No Absorption From Gas Streams With Tertiary Organic Hydroperoxide Solutions, Huihong Ao

Theses

The selective removal of nitric oxide from gas streams was investigated using 3,6-dimethyl-3-octyl hydroperoxide, p-menthane hydroperoxide, pinane hydroperoxide, and cumene hydroperoxide in solutions of n-hexadecane (cetane). The influence of different parameters such as temperature, gas stream flow rate (or residence time), and concentration of hydroperoxide compounds on efficiency of NO removal was evaluated. The basis of this research was to duplicate atmospheric reactions between hydroperoxides and NO in order to produce NO₂. We succeeded in removing NO from gas streams, but failed to produce NO₂. NO reacted with the hydroperoxides to produce nitrates. These nitrates are …

I. Removal Of Chromium From A Highly Contaminated Soil/Slag Matrix By Soil Washing At Low Ph, Ii. Removal Of Chromium From Impregnated Clay Matrices By Soil Washing At Low Ph, Erez Gotlieb

Theses

Section I. Chromium is a major soil contaminant of industrial sites in New Jersey, as well as in many of the Superfund sites throughout the United States. Removal of chromium by soil/slag washing with low pH sulfuric acid solutions is described. The extraction parameters are acid concentration, contact time, temperature, solvent/soil ratio, and acid type. The effect of two-stage extraction is discussed.

Soil/slag washing with sulfuric acid concentrations of 2% weight:volume (units are g/ml. This concentration is approximately equal to 0.4 N) at 75:1 v:w solvent/soil ratios yielded chromium extraction efficiencies of 95%, but 50% of the soil matrix was …

Remote Sensing Of On-Road Vehicle Emissions, Donald H. Stedman, Gary A. Bishop, Paul L. Guenther, James E. Peterson, Stuart P. Beaton, Iain F. Mcvey

Fuel Efficiency Automobile Test Publications

No abstract provided.

Partial Characterization Of The Major Lipooligosaccharide From A Strain Of Haemophilus Ducreyi, The Causative Agent Of Chancroid, A Genital Ulcer Disease, William Melaugh, Nancy J. Phillips, A A. Campagnari, R Karalus, B W. Gibson

Chemistry Faculty Publications

The first preliminary structure of a surface lipooligosaccharide from Haemophilus ducreyi has been determined. The major oligosaccharide was released by mild acid hydrolysis and analyzed by liquid secondary ion and tandem mass spectrometry. The mass spectral data combined with composition and methylation analysis yielded the most probable structure; Gal1----4GlcNAc1----3Gal1----4Hep1----6Glc1----( Hep1----2Hep1----)3,4Hep1---- KDO, where the reducing terminal 3-deoxy-D-manno-octulosonic acid (or KDO) exists in an anhydro form. This anhydro species results from the elimination of a phosphate from C-4 of KDO during mild acid hydrolysis. The core heptose trisaccharide consists of L-glycero-D-manno-heptose, but analysis of the peracetylated sugars indicated that the 1,4-linked heptose …

Solid-State Nmr Characterization Of Organics In Cement, Michael A. Janusa

Faculty Publications

Solid-state magic angle spinning nuclear magnetic resonance (MAS NMR) has been applied to cement samples containing water-soluble organics, ethylene glycol, phenol, p­bromophenol and p-chlorophenol. Cement matrix development has been followed by ²⁹Si and²⁷Al NMR, which shows the organics, particularly ethylene glycol, to be promoters of silicate polymerization despite the fact that they reduce the compressive strength of the pastes. ¹³C NMR shows that phenol is completely ionized in cement pastes, but with substituted phenols in the presence of extra added metal salts, ionization is not always complete. ²H NMR on d_{5 …}

Characterization And Implementation Of A Continuos Flow Trace Metal Preconcentration System For Inductively Couples Plasma Atomic Emission Spectrometry, Robert N. Sibley

Senior Scholar Papers

A continuous flow pre-concentration system for analysis of trace metals in natural waters was characterized and used to determine the copper(II) and lead(II) concentrations in seawater from Penobscot Bay, Maine. Pre-concentrated samples were analyzed by inductively coupled plasma atomic emission spectrometry (ICP-AES). System characterization involved elucidation of the thermodynamic complexation constants, KCu(II) and KPb(II), for Cu(II) and Pb(II) with the pre-concentration column chromatographic material. This was done in aqueous media of known pH and ionic strength. The column contained 8-hydroxyquinoline immobilized on Toyopearl HW-75 fractogel chromatographic resin. The buffer system used for metal binding experiments was an equimolar mixture of …

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.

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 Casscf Study Of Various Rotamers Of The Hexatriene Radical Cation, Robert J. Cave, Jenifer L. Johnson

All HMC Faculty Publications and Research

Results are presented from ab initio calculations on the ground and two low-lying excited states of the hexatriene radical cation in a variety of stable conformations of the electronic ground state of the molecule. We have performed Hartree-Fock geometry optimizations using the STO-3G and 6-31g basis sets and have performed vibrational analyses for all stable conformers in the 6-31G basis. In addition, we have performed geometry optimizations in both basis sets using CASSCF wave functions where the five π electrons are correlated. No new geometrical information is obtained at this level of treatment. Excitation energies to the two lowest-lying doublet …

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 …

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 …}

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 …

A Proposal For United States/Polish Collaboration On Energy And The Environment, Carole B. Szpunar

Chemistry: Faculty Publications and Other Works

Argonne National Laboratory, a U.S. Department of Energy facility that is operated by the University of Chicago and located southwest of Chicago, Illinois, has proposed a collaborative effort by the United States and Poland to conduct applied research on energy and environmental topics of common interest. Through this collaboration, evaluative studies on energy and environmental assessment issues could be developed and implemented by Argonne and one or more sister institutions in Poland, which could lead to active research, development, and demonstration joint activities. The objective of this initiative is to produce strategies and options for review by Poland's decision makers …

The Eukaryotic Initiation Factor 2-Associated 67-Kda Polypeptide (P67) Plays A Critical Role In Regulation Of Protein Synthesis Initiation In Animal Cells, Manas K. Ray, Bansidhar Datta, Arup Charkraborty, Ansuman Chattopadhyay, Susanne Meza-Keuthen, Naba K. Gupta

Department of Chemistry: Faculty Publications

The eukaryotic initiation factor 2 (eIF-2)- associated 67-kDa polypeptide (p⁶⁷) isolated from reticulocyte lysate protects the eIF-2 α subunit from eIF-2 kinase-catalyzed phosphorylation and promotes protein synthesis in the presence of active eIF-2 kinases. We have now studied the roles of p⁶⁷ and eIF-2 kinases in regulation of protein synthesis using several animal cell lysates and an animal cell line (KRC-7) in culture under various growth conditions. The results are as follows. (i) Both p⁶⁷ and eIF-2 kinase(s) are present in active forms in all animal cells under normal growth conditions and p^{67 …}

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

Master's Theses

No abstract provided.

Multinuclear Magnetic Resonance Study Of Chlorine And Cesium Ion Distribution In Human Erythrocyte Suspensions, Lisa Wittenkeller

Dissertations

No abstract provided.

Palladium(Ii) Catalysis, Glenn Noronha

Dissertations

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 …

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 …

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

Thalamic Stroke: Presentation And Prognosis Of Infarcts And Hemorrhages, Wolfgang Steinke, Ralph L. Sacco, J. P. Mohr, Mary A. Foulkes, Thomas K. Tatemichi, Philip A. Wolf, Thomas R. Price, Daniel B. Hier

Chemistry Faculty Research & Creative Works

Thalamic Strokes in 62 Patients Selected from the Stroke Data Bank Were Studied to Determine Differences among 18 Infarctions (INF), 23 Localized Hemorrhages (ICH), and 21 Hematomas with Ventricular Extension (IVH). Stupor or Coma at Onset Occurred More Frequently in the IVH (62%) Than in the INF (6%) or ICH (13%) Groups and Was Reflected in Significantly Lower Median Glasgow Coma Scores in the IVH Group (7) Than in the INF (15) and ICH (14) Groups. Although Ocular Movements Were More Frequently Abnormal in the IVH Group Compared with the ICH and INF Groups, No Significant Differences Were Found in …

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 …

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.

Early Clinical Differentiation Of Cerebral Infarction From Severe Atherosclerotic Stenosis And Cardioembolism, S. G. Timsit, R. L. Sacco, J. P. Mohr, M. A. Foulkes, T. K. Tatemichi, P. A. Wolf, T. R. Price, D. (Daniel) B. Hier

Chemistry Faculty Research & Creative Works

Background and Purpose: Hyperacute Cerebral Infarction Trials Require Early Differentiation of Infarction Subtype. Our Aim Was to Determine Clinical Factors Predictive of Infarction Subtype from Data Collected in the Early Hours of Admission. Methods: using the 1,273 Patients Enrolled in the Stroke Data Bank, Stroke Risk Factors and Demographic, Clinical, and Radiological Features Were Compared between the 246 Cardioembolic and 113 Large-Vessel Atherosclerotic Cerebral Infarcts. Results: Stroke Data Bank Definitions Ensured More Transient Ischemic Attacks in Atherosclerotic Infarcts and More Cardiac Disease in Cardioembolic Infarcts, But the Diagnosis Was Distinguished Further using a Logistic Regression Model. Fractional Arm Weakness (Shoulder …

1-Ferrocenyl-1-Cyclopropyl Cation: The First Long-Lived Cyclopropyl Cation, G. K.Surya Prakash, Herwig Buchholz, V. Prakash Reddy, Armin De Meijere, George A. Olah

Chemistry Faculty Research & Creative Works

No abstract provided.

Low Temperature Spectroscopic And Annealing Studies Of Disordered Organic Solids, Dwayne L. Labrake

Dissertations

No abstract provided.

Hydration Behavior Of Laser Dye Aerosols Of Mixed Composition Having High Critical Supersaturations, Max B. Trueblood, Donald E. Hagen, Darryl J. Alofs

Mechanical and Aerospace Engineering Faculty Research & Creative Works

This Study Concerns Aerosol Particles of Mixed Composition. the Particles Contain a Water Insoluble Core (Polystyrene Latex), Surrounded by a Water Soluble Shell (Various Fluorescent Dyes). a Collison Nebulizer and an Electrostatic Aerosol Classifier Are Used to Prepare the Aerosol; its Critical Supersaturation Spectrum is Measured with a Diffusion Cloud Chamber. Experiments Were Done using Four Different Dyes (Disodium Fluorescein, Sulforhodamine 640, Sulforhodamine B and Rhodamine 560 Chloride) with Five Different Polystyrene Latex Sphere Sizes. the Results Indicate that a Kohler-Type Behavior is Obeyed. This Technique of Putting a Soluble Coating Onto an Insoluble Core is Found to Be a …

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

Faculty Publications

No abstract provided.