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A Scc Mo Calculation On The Tetracyanoethylene-Benzene Complex, Joe Kirsch, Shannon Lieb, Mark Cisneros

Scholarship and Professional Work - LAS

Dr. Shannon Lieb's contribution to Volume 94 of the Proceedings of the Indiana Academy of Science.

Soil Acidity On High Rainfall Pastures, J S. Yeates, D. A. Mcghie, I. R. Wilson

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

Most soils of the high rainfall area of south-western Western Australia are naturally acis.

The most acid group of soils, the peaty sands. have been routinely limed before subterranean clover pastures were established since research in the 1950s showed that poor Rhizobium nodulation could be overcome with the application of about 2 tonnes per hectare of coastal limesand.

Soil Acidity In The Eastern Wheatbelt, W M. Porter, I. R. Wilson

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

In Western Australia parts of the sandplain of the eastern wheatbelt are very acid and produce poor crops, It was not until the late 1970s that the effect of soil acidity on the productivity of the sandplain soils was examined in any detail.

Since then researchers have learnt a great deal about the nature of soil acidity in the eastern wheatbelt sandplain soils and can suggest management options for farmers.

This article discisses the problem of the very acid soils. It does not deal with the moderately acid, medium textured soils of the eastern wheatbelt. Although the acidity of these …

A Two Part Research Report: Aromatic Nucelophilic Fluoroal Koxylation Via Cationic Phase Transfer Catalysis And Reactions Of Unsymmetrical Vinamidinium Salts With Organometallic Reagents, Joseph E. Coury

Retrospective Theses and Dissertations

This report discusses research which was conducted in two areas: the study of aromatic nucleophilic fluoroalkoxylation assisted via cationic phase transfer catalysis and the study of unsymmetrical vinamidinium salts and their reactions with organometallic reagents.

Sodium alkoxides have been successfully used to fluoroalkoxylate activated halo- aryl and heteroaryl substrates under phase transfer catalysis conditions. Optimum reaction conditions incorporated tetra-n-butyl-phosphonium bromide as the catalyst and refluxing toluene as the solvent medium. Different quarternary phosphonium and arrmonium salts have been evaluated as catalysts: also, the effects of activating groups, leaving groups, and nucleophiles have been reported.

The reaction of 3-dimethylamino-3-phenyl-prop-2-en-l-ylidendimethyliminium perchlorate with …

A Three Part Research Report: The Synthesis Of Potential Insecticides, N-(4-Heteroaryloxybenzoyl)-N'-(2,4-Dichlorobenzoyl) Hydrazines: A Reinvestigation Of Hexamethylphosphoramide With Ketoximes; Regioselective Fluoralkoxylation And Polyfluoroalkoxylation Of Activated Dihalobenzenes And Dihaloheterocycles, Gary A. Decrescenzo

Retrospective Theses and Dissertations

This report discusses research in three areas of organic synthesis: The synthesis of potential insecticides; the reinvestigation of the reaction of hexamethylphosphoramide with ketoximes; and the regioselective fluoroalkoxylation and polyfluoroalkoxylation of activated dihalobenzenes and dihaloheterocycles. In Part I, a series of N-(4-heteroaryloxybenzoyl)-N'-(2, 3-dichlorobenzoyl) hydrazines are synthesized, and attempts at cyclic dehydration to the corresponding 2, 5-disubstituted-1, 3, 4-oxadiazoles are discussed. In Part II, the synthesis of N, N-dimethyl-N'-aryl amidines by the reaction of aryl alkyl and diaryl ketoximes with HMPA is discussed. In Part III, a series of activated dihalobenzenes and dihaloheterocycles are reacted with sodium trifluoroethoxide to study the …

Oxidation Of Valencene To Nootkatone, Tung F. Chen

Retrospective Theses and Dissertations

The liquid phase autoxidation of the readily available sesquiterpene valencene to the commercially important perfuming agent nootkatone utilizing gaseous oxygen at atmospheric pressure has been investigated. Catalyst systems involving transition metal salts and complexes, and phase-transfer catalysts have been evaluated under different conditions of valencene concentration, catalyst concentration, reaction temperature, solvent and oxygen flow rate. Of eighteen candidate catalysts for the oxidation of valencene to nootkatone, chlorocarbonylbis (triphenylphosphine) iridium (Vaska's catalyst) demonstrated good activity and appeared to show the best potential for future work.

Soil Acidity And Liming In The Lower Great Southern, R N. Glencross, M. G. Clarke

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

In the 375 to 750 millimetre rainfall area of the Lower Great Southern, reports of loss of subterranean clover from established pastures, reduced carrying capacity for sheep and increasing soil acidity lead to the establishment in 1981 of a research programme into the effects of soil acidity on pasture productivity in that region.

A Re-Examination Of The Reactions Of Cyanide With Cytochrome C Oxidase, M. G. Jones, D. Bickar, M. T. Wilson, M. Brunori, A. Colosimo, P. Sarti

Chemistry: Faculty Publications

Experiments were performed to examine the cyanide-binding properties of resting and pulsed cytochrome c oxidase in both their stable and transient turnover states. Inhibition of the oxidation of ferrocytochrome c was monitored as a function of cyanide concentration. Cyanide binding to partially reduced forms produced by mixing cytochrome c oxidase with sodium dithionite was also examined. A model is presented that accounts fully for cyanide inhibition of the enzyme, the essential feature of which is the rapid, tight, binding of cyanide to transient, partially reduced, forms of the enzyme populated during turnover. Computer fitting of the experimentally obtained data to …

The Intermolecular Force Field Of Acetylene-Hcl: The Normal Coordinate And Centrifugal Distortion Analysis Of Two Weakly Bound Rigid Rods, Rebecca S. Lee

Masters Theses

In order to determine the intermolecular force field of C₂H₂⋅⋅HCl, a normal coordinate analysis appropriate for two weakly bound rigid rods is developed. An exact centrifugal distortion analysis is then carried out on the microwave spectrum of this "T''-shaped hydrogen-bonded π complex. The distortion constants and published matrix-isolated vibrational frequencies are employed in the normal coordinate analysis to obtain the intermolecular force field and refinements in the structural parameters. The following van der Waals force field is found to reproduce the existing spectroscopic constants of C₂H₂⋅⋅H³⁵Cl … . This study …

The Purification And Partial Characterization Of The Surface Polysaccharides From Three Fast-Growing Rhizobium Japonicum Strains, Madhav P. Yadav

Masters Theses

The fast-growing strains of R. japonicum were originally isolated from China. They are acid-producing Rhizobia and are capable of nodulating soybeans. These isolates share a common host-specificity (Peking soybean) with the slow-growing R. japonicum strains even though their biochemical properties are more closely related to other fast-growing Rhizobium species. The surface polysaccharides from three fast-growing R. japonicum strains--USDA201, USDA205, and HC205--were isolated and partially characterized. Strain HC205 is a nod⁻ mutant of USDA205 which lacks the symbiotic plasmid. These surface polysaccharides consist of extracellular, capsular and lipopolysaccharides (EPSs, CPSs and LPSs). The EPSs from all three strains are very similar …

Comparison Of Three Methods For Sampling Fishes And Macroinvertebrates In A Vegetated Wetland, B. J. Freeman, H. S. Greening, J. Douglas Oliver

Faculty Publications and Presentations

Three methods of sampling fishes, two seining methods and a drop trap method, were evaluated in heavily vegetated freshwater habitats. The portable drop trap method, which utilized a 1 x 1 m-sq. trap, collected significantly more macroinvertebrates and fish per unit area than did the seining methods. The meter square drop trap offered the additional advantages of a greater number of animals per unit effort and an integrated sample of vegetation, macroinvertebrates and fish in a given area. A 90% (s.d.= 7.4%) recovery of tagged fishes released into the traps in different habitats showed the m2 drop trap to be …

Modeling Of Laboratory Scale Batch Distillations With A Desktop Computer, Dale F. Johnson

Retrospective Theses and Dissertations

A program has been written that simulates the operation of a batch distillation process. The program has been implemented on a Hewlett-Packard 9845T minicomputer and will be used as an instructional aid in a graduate level chemistry course. The program is very user interactive and is capable of using the final conditions from one run as the initial values of the next simulation. The batch simulation is achieved by using a tray-by-tray algorithm and is equipped with three integration techniques; the Euler, the Modified Euler and the 4th order Runge-Kutta methods. The program has the capability for studying the effect …

Sulphur Needs Of Crops And Pastures, J S. Yeates

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

Sulphur deficiency has long been recognised as a potential problem of legume pastures in the higher rainfall areas (over 750 mm a year) of south-west Western Australia. Before the introduction of granulated superphosphate (about 1970), sulfer deficiencies commonly developed in spring on susceptible soils despite autumn applications of superphosphate (containing about 10.5 per cent sulphur).

In loww and medium rainfall areas sulphur deficiency is rarely reported, at least partly because of annual superphosphate applications. However large areas of the sandy-surfaced soils of Western Australia would become sulphur deficient for pastures and crops if sulphur inputsd in fertilisers were substantially reduced. …

I :Synthesis And Evaluation Of Polymer Supported Homogenous Oxidation Catalysts. Ii: Synthesis And Evaluation Of Polymer Supported Multi Site Phase Transfer Catalysts Iii: Synthesis Of Potential Herbicides, Russell L. Leonard

Retrospective Theses and Dissertations

This report consists of three parts. Part I involved the synthesis and evaluation of some polymer supported homogeneous oxidation catalysts – specifically, the synthesis of polystyrene 2(bis-salicylaldehyde) 2-methyl propylene-1, 3-diiminato cobalt (II) and polystyrene 2(bis-2, 4-pentanedione) 2-methyl propylene-1, 3-diiminato cobalt (II). Part II involved the synthesis of both soluble and insoluble phase transfer catalysts designed to catalyze nucleophilic substitution reactions. Trisite quaternary phosphonium and disite quaternary phosphonium salts were prepared. Part III involved the synthesis of several potential herbicides.

Part I: The Synthesis Of Potential Agrochemicals. Part Ii: The Use Of Gold's Reagent As A Lynch Pin In The Formation Of Five And Six Membered Heterocycles, Keith F. Correia

Retrospective Theses and Dissertations

This research report focuses on two topics: the synthesis of potential agrochemicals and the use of Gold's reagent as a lynch pin to form five- and six-membered heterocycles. A diacyl hydrazide and two oxadiazoles are prepared for use as possible insecticides. Gold's reagent behaves as a one-atom and two-atom lynch pin when reacted with 1, 4- and 1, 5-dinucleophiles, respectively. Reaction conditions, interpretation of spectral data, and recommendations for further research are provided.

Evaluation Of Sugar Cane Bagasse And Rice Straw As Process Substrates For The Production Of Ethyl Alcohol, Douglas B. Rivers, Gisella M. Zanin, George H. Emert

Journal of the Arkansas Academy of Science

No abstract provided.

Aphasia After Left Thalamic Infarction, Philip B. Gorelick, Daniel B. Hier, Louis Benevento, Susan Levitt, Walter Tan

Chemistry Faculty Research & Creative Works

We Examined a 70-Year-Old Woman Who Became Aphasic after a Left Thalamic Infarction. Computed Tomographic Scan Showed Injury that Was Largely Limited to the Ventral Anterior and Rostral Ventral Lateral Thalamic Nuclei. Speech Was Characterized by Reduced Voice Volume, Impaired Auditory and Reading Comprehension, Perseverations, Intermittent Use of Jargon, Fluctuations in the Ability to Perform Confrontation Naming, Extraneous Intrusions, Verbal Paraphasia, Intact Repetition Skills, and Fluent Speech that Was Laconic But Grammatically Correct. We Propose that the Deficits after Left Thalamic Injury Can Be Grouped into the Following Four Large Clusters: Extrapyramidal Deficits (Decreased or Fading Voice Volume), Deficits in …

Carbon Monoxide-Driven Reduction Of Ferric Heme And Heme Proteins, D. Bickar, C. Bonaventura, J. Bonaventura

Chemistry: Faculty Publications

Oxidized cytochrome c oxidase in a carbon monoxide atmosphere slowly becomes reduced as shown by changes in its visible spectra and its reactivity toward oxygen. The 'autoreduction' of cytochrome c oxidase by this procedure has been used to prepare mixed valence hybrids. We have found that this process is a general phenomenon for oxygen-binding heme proteins, and even for isolated hemin in basic aqueous solution. This reductive reaction may have physiological significance. It also explains why oxygen-binding heme proteins become oxidized much more slowly and appear to be more stable when they are kept under a CO atmosphere. Oxidized α …

A Theoretical And Experimental Examination Of Sodium Chloride Hydration, Debra Conway Modra

Dissertations and Theses

A Hitachi Hu 125C transmission electron microscope in which the standard specimen holder was replaced by an environmental cell was used to observe the hydration of sodium chloride crystals. To observe Kelvin curvature and solubility effects sodium chloride crystals which were 0.1u or smaller were of special interest. An electrohome video system attached to the electron microscope was used to record the sodium chloride hydration for subsequent particle measurement and viewing.

A theoretical model was also developed. Thermodynamic properties such as the Kelvin curvature and solubility effects were considered as well as the kinetic expressions for salt dissolution/recrystalization and water …

Molecular Motion And Phases In An Equimolar Phosphatidylcholine/Ethylene Glycol System, David W. Larsen, Shankar B. Rananavare, Frank E. Stary, Magda Elnokaly, Stig Friberg

Chemistry Faculty Research & Creative Works

An equimolar mixture of phosphatidylcholine and ethylene glycol was studied by pulsed proton NMR at temperatures between 100 and 430 K. Relaxation times T1, T1ρ, and T1D, and second moments, M2, were measured. The system is lamellar liquid crystalline at room temperature, but at least four phases are present within the temperature range studied. Phase transitions were confirmed by DSC. Activation barriers were estimated for methyl reorientation, choline group motion, and chain motion. Models to describe the various motions and the role of spin diffusion are discussed. The relationship of the parameters for the present system to those for the …

Solubilization Of Calcium Dodecyl Sulfate In A Micellar Solution And In Lamellar Liquid Crystal, Stig Friberg, David W. Osborne

Chemistry Faculty Research & Creative Works

Calcium dodecyl sulfate (CDS) was solubilized in the aqueous micellar solution of sodium dodecyl sulfate and in the lamellar liquid crystal obtained from water, sodium dodecyl sulfate and decanal. The solubilization of CDS in the micellar solution was strongly increased with the concentration of sodium dodecyl sulfate while the maximum amount of CDS solubilized in the liquid crystal remained similar. The solubilization in the micellar solution was gradually increased with the alcohol content with a sudden reduction to zero at the decanol/sodium-dodecyl-sulfate ratio marking the end of the micellar region with no calcium soap being present. The dependence of the …

A Lamellar Liquid Crystal As An In Situ Surface Balance. I. The Conformation Of 5- (And 6-)Carboxy-4-Hexyl-2-Cyclohexene-1-Yl Octanoic Acid And Its Monosoap, Tony Flaim, Stig Friberg

Chemistry Faculty Research & Creative Works

The interfacial conformation of a dicarboxylic acid, 5- (and 6-)carboxy-4-hexyl-2-cyclohexene-1-yl octanoic acid, and its monosodium soap was determined from the change of liquid crystal dimensions after introduction of the diacid compounds. The results showed that both functional groups of the Mono soap form were present at the interface and that increased water content of the liquid crystal matrix had little effect on the conformation of the Mono soap. On the other hand, the results indicated the conformation of the diacid as such to depend on the water content of the matrix. At low water content, the diacid form was in …

Alignment Of A Nonaqueous Lyotropic Liquid Crystalline Phase With Lecithin, David W. Larsen, Shankar B. Rananavare, Stig Friberg

Chemistry Faculty Research & Creative Works

No abstract provided.

Magnetic And Crystallographic Structure Of Y₆Mn₂₃D₂₃, K. A. Hardman-Rhyne, James J. Rhyne, E. Prince, Cyrus E. Crowder, William Joseph James

Chemistry Faculty Research & Creative Works

The magnetic behavior of Y6Mn23 is dramatically altered upon hydrogenation (or deuteration). In this study it has been found, by means of high-resolution powder diffraction and Rietveld refinement techniques, that the crystallographic structure is distorted from face-centered cubic (Fm3m) at 295 K to a primitive tetragonal structure at 4 K in which deuterium atoms are atomically ordered. Y6Mn23 is a ferromagnetic compound with Tc=486 K, and bulk magnetization of 13.2 Bf.u. (formula unit). After deuteration of Y6Mn23 to the composition Y6Mn23D23, low-temperature scattering data (T<180 K) show that the b and f2 sites in the Fm3m structure are antiferromagnetic and the d and f1 sites have no spontaneous magnetic moment. © 1984 The American Physical Society.

Effects Of N-Substituents On The Polymerization Properties Of Maleimide, Dilip R. Abayasekara

Theses and Dissertations

The effect of the amide function and the carbethoxy function on the polymerization properties of maleimide are reported. The effects of these functions on homopolymerization and copolymerization (with styrene) were examined. These electron-withdrawing groups appeared to decrease the rate of homopolymerization and increase the rate of copolymerization.

N-carbamylmaleimide and N-carbethoxymaleimide were copolymerized with styrene in 1,4 -dioxane at 60.0° C at different feed ratios to high conversion. Copolymer composition, determined by elemental analysis and 1H NMR, indicated that while 1:1 copolymers were obtained with an equimolar feed ratio, the two systems were not alternating. It is of note that the …

A Study Of Oxygen Functional Groups In Illinois Coal Fractions, Kenneth R. Osborne

Masters Theses

Ferric chloride/acetic anhydride reacted with butyl phenyl ether in acetonitrile at 80° to give a 75.6% yield of p-butoxyacetophenone. Reactions with benzyl aryl ethers gave 30% cleavage. The reaction of benzyl phenyl ether gave 10.3% p-benzyloxyacetophenone as well as cleavage product. Reaction of a pyridine soluble, toluene insoluble fraction (preasphaltene) of an Illinois No. 6 coal with ferric chloride/acetic anhydride in acetonitrile gave a product 94% insoluble in pyridine. The insolubility was ascribed to condensation reactions.

Phenols were measured in coals, preasphaltenes and preasphaltene derivatives by acetylation with acetic anhydride in pyridine. Suggestions for improvement in the method were presented. …

Mechanism Of Translational Control By Partial Phosphorylation Of The Α Subunit Of Eukaryotic Initiation Factor 2, John Siekierka, Veeraswamy Manne, Severo Ochoa

Department of Chemistry and Biochemistry Faculty Scholarship and Creative Works

Catalysis of ternary complex formation by the GDP exchange factor (GEF), in the presence of Mg2+, is blocked by phosphorylation of the α subunit of the eukaryotic initiation factor 2 (eIF-2). We proposed earlier that this phosphorylation interferes with the interaction between eIF-2 and GEF (then termed ESP). If so, inhibition should be related to the extent of phosphorylation. However, work in other laboratories indicated that in fully inhibited, heme-deficient lysates only 20-40% of the EIF-2 is phosphorylated. To understand the nature of the molecular lesion in eIF-2-α phosphorylation we used a system of pure components in which the rate …

Copper And Barium As Dietary Discriminants: The Effects Of Diagenesis, J B. Lambert, S V. Simpson, Carole B. Szpunar, J E. Buikstra

Chemistry: Faculty Publications and Other Works

In skeletons excavated from Woodland sites, copper and barium levels are found to have been contaminated by influx from the soil environment. Electron microprobe scans for both elements show build-up along the outer surface of femur cross sections. Elemental levels for Cu and Ba are lower in the femur or fibula than in the more porous rib. The distribution of Cu in the immediately surrounding soil is highly anisotropic. These observations indicate that Cu and Ba should not be used for dietary inferences about ancient populations without independent evidence that diagenesis is not important.

Totally Empirical Wavefunctions From X-Ray Diffraction Data, Martin Jeffry Goldberg

Dissertations, Theses, and Capstone Projects

The interpretation of coherent x-ray diffraction experiments by a quantum model is described. Adjusting the coefficients of an LCAO expansion to best fit measured Bragg intensities results in a totally empirical quantum wavefunction. The quantum model is compared to a multipole expansion. The constraints imposed by quantum mechanics are examined, and several methods of satisfying these constraints while best fitting a wavefunction to measured Bragg intensities are detailed. Application is made to beryllium metal, with a resultant fit R(,1) = .00249. Similar applications to graphite and diamond are outlined. The formalism is extended to explicitly include solid-state effects, and this …

Lyotropic Liquid Crystals From Lecithin, Water, And Polyethylene Glycol, Magda El Nokaly, Stig Friberg, David W. Larsen

Chemistry Faculty Research & Creative Works

Lyotropic liquid crystals with lecithin as the amphiphile and with water/polyethylene glycol (PEG) solutions as the solvent were prepared with polyethylene glycol/water ratios from 182 to 0. The liquid crystals were lamellar and the interlayer spacing was independent of the solvent content for water/PEG ratios ≤1 but increased strongly with the water/PEG ratio. Higher ratios gave increased interlayer spacing with solvent content similar to the variation for liquid crystals with water as solvent but the absolute values of the spacing were higher. © 1984 Academic Press, Inc. All rights reserved.