Physical Sciences and Mathematics Commons^™

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.

Composition Of Regenerated Cell Walls Of Reverting Aureobasidium Pullulans Protoplasts, D. R. Quigley, Donald J. Siehr

Chemistry Faculty Research & Creative Works

Protoplasts of Aureobasidium pullulans, formed by treating normal blastospores with polysaccharide-hydrolizing enzymes, synthesized glycans when incubated in shallow culture. The polysaccharides formed a loose, thick coating on the cells. The glycans that were formed are similar to the glycans in normal cell walls; however, they lack the branching that is normally found. This result is consistent with the findings of others who have studied the cell wall composition of reverting yeast protoplasts.

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 …

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 …

Single Compound Forming A Lyotropic Liquid Crystal At Room Temperature, Stig Friberg, Paul Liang, Frances E. Lockwood, Maher Tadros

Chemistry Faculty Research & Creative Works

The compound triethanolammonium oleate forms a lamellar liquid crystal at room temperature. The basis for the lyotropic mesomorphism is the fact that part of the triethanolammonium oleate has changed to triethanolamine and oleic acid. These two compounds serve as solvents in the liquid crystalline structure. © 1984 American Chemical Society.

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.

Protein Synthesis In Rabbit Reticulocytes: A Study Of The Mechanism Of Action Of The Protein Factor Rf That Reverses Protein Synthesis Inhibition In Heme-Deficient Reticulocyte Lysates, M. Grace, M. Bagchi, F. Ahmad, T. Yeager, C. Olson, I. Chakravarty, N. Nasrin, A. Banerjee, N. K. Gupta

Chemistry Department: Faculty Publications

A eukaryotic initiation factor 2 (eIF-2)-ancillary protein factor Co-eIF-2 promotes displacement of GDP from eIF-2GDP and facilitates ternary complex (Met-tRNA_f• eIF-2-GTP) formation in the presence of Mg²⁺. Heme-regulated protein synthesis inhibitor, HRI, phosphorylates the α-subunit of eIF-2 and thus inhibits ternary complex formation as Co-eIF•2 does not displace GDP from eIF-2α(P)•GDP. RF, a high molecular weight cell supernatant factor, reverses protein synthesis inhibition in heme-deficient reticulocyte lysates and also reverses HRI inhibition of ternary complex formation. RF contains Co-eIF•2 activity. In addition, an active RF preparation contains excess α-subunit of eIF-2 in the free and unphosphorylated …

The Structure Of 1-Tert-Butyl-2,2,3,4,4-Pentamethylphosphetane 1-Oxide, C12H25Op, J. A. Campbell, C. N. Caughlan, A. Fitzgerald, C. Campana, Sheldon E. Cremer

Chemistry Faculty Research and Publications

No abstract provided.

Nmr Measurements On Intercalated 3r-Tas2.Ix (I=Nh3 And N2h4), N. H. Handly, Juana Vivó Acrivos

Juana Vivó Acrivos

No abstract provided.

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 …

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.

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 …

Measurement Of Low Vapor Pressures : A Kinetic Approach, Samuel Bernard Bliden

Dissertations and Theses

A kinetic model was applied to vapor pressure data obtained by a variable flow method. The vapor pressures of benzoic acid, naphthalene, benzophenone, and phenylhydrazine were measured at temperatures of 293K to 307K. The data are summarized in the data table on the following page. These data were obtained by passing air over a sample of the substance in a tube. The air stream was combusted, and a flame ionization detector was used to measure the mass of CO₂ so obtained. Several different flow rates were used at each temperature with each substance.

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.

Studies Of Dispersion Energy In Hydrogen‐Bonded Systems. H2o–Hoh, H2o–Hf, H3n–Hf, Hf–Hf, M. M. Szczesniak, Steve Scheiner

Chemistry and Biochemistry Faculty Publications

Dispersion energy is calculated in the systems H₂O–HOH, H₂O–HF, H₃N–HF, and HF–HF as a function of the intermolecular separation using a variety of methods. M≂ller–Plesset perturbation theory to second and third orders is applied in conjunction with polarized basis sets of 6‐311G∗∗ type and with an extended basis set including a second set of polarization functions (DZ+2P). These results are compared to a multipole expansion of the dispersion energy, based on the Unsöld approximation, carried out to the inverse tenth power of the intermolecular distance. Pairwise evaluation is also carried out using both atom–atom …

Proton Transfers Between First‐ And Second‐Row Atoms: (H2ohsh2)+ And (H3nhsh2)+, Steve Scheiner

Chemistry and Biochemistry Faculty Publications

Ab initio molecular orbital methods are used to study the transfer of the central proton along the hydrogen bonds in (H₂OHSH₂)⁺ and (H₃NHSH₂)⁺. Proton transfer potentials are generated using the 4‐31G∗ basis set at the Hartree–Fock level for various values for the hydrogen bond length R(XS). Full geometry optimizations are carried out at each stage of proton transfer. The barrier to proton transfer increases as the hydrogen bond is lengthened. For a given bond length, the highest barriers are observed for transfer from …

Ab Initio Comparison Of H Bonds And Li Bonds. Complexes Of Lif, Licl, Hf, And Hcl With Nh3, Z. Latajka, Steve Scheiner

Chemistry and Biochemistry Faculty Publications

Ab initio calculations are carried out on the complexes H₃N–LiF, H₃N–LiCl and their analogs H₃N–HF and H₃N–HCl as well as the isolated subunits. Double‐zeta basis sets, augmented by two sets of polarization functions, are used in conjunction with second‐order Moller–Plesset perturbation theory (MP2) for evaluation of electron correlation effects. The Li bonds are found to be substantially stronger than their H‐bonding counterparts, due in large measure to the greater dipole moments of the LiX subunits. Correlation has a large effect on the geometry and energetics of …

A New Method For The Quantitative Determination Of Radon-222 In Natural Waters, Charles Whitlow

Honors Theses

Several studies in the past have shown radon to be present in many natural waters including mineral springs, hot springs, rivers, lakes, and rainwater. A compilation of tables of radon concentration in mineral and hot springs all over the world was published by Kuroda in 1953. Most of this radon comes from radium and uranium minerals which the springs flow over. The radon concentration in lakes is from two major souces [sic]. One source is dissolved radium and the other is the inflow of high radon concentration groundwaters [sic].

An Approach To The Synthesis Of Pyrans, Thomas F. Ball

Dissertations, Theses, and Masters Projects

No abstract provided.

Transition Metal Promoted Carbometallation Of Alkynols, Douglas W. Moore

Dissertations, Theses, and Masters Projects

No abstract provided.

Magnetic And Mössbauer Study Of Metal‐Zeolite Interaction In Catalysts, Thomas Pannaparayil, M. Oskooie-Tabrizi, C. Lo, L. N. Mulay, G. A. Melson, V. U. S. Rao

Chemistry Publications

Molecular sieve aluminosilicates, such as ZSM‐5 and mordenite, when impregnated with highly dispersed Fe, yield catalysts for the selective conversion of coal‐derived syngas (CO+H₂) to liquid hydrocarbon fuels. Fe performs the primary Fischer‐Tropsch (FT) syngas to yield light olefins which are converted by the acidic (H⁺) and shape‐selective function of the zeolite to high octane gasoline components. The physical aspects of the Fe‐mordenite interaction studied by magnetic measurements, Mössbauer, and IR spectroscopy are reported and correlations with the catalytic properties are drawn. Mordenite samples with [SiO₂/Al₂O₃] ratio in the range …

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.

Order Parameters Of Hydrocarbons Solubilized In A Lamellar Liquid Crystal, Anthony J.I. Ward, Stig Friberg, David W. Larsen, Shankar B. Rananavare

Chemistry Faculty Research & Creative Works

A preliminary study of the 2H NMR spectrum of n-hexadecane-d34 solubilized in the lamellar phase of tetra ethylene glycol n-dodecyl ether has been made as a function of solubilization content. Complex spectra comprising eight overlapping powder spectra were observed, which showed a complex oil concentration dependence. These spectra were unusually rich in detail and indicate a considerably higher degree of complexity than has earlier been reported for solubilized hydrocarbons. The derived order profile was found to be different from that normally found for amphiphiles in lamellar environments. A tentative model involving some penetration of solubilize molecules between the host amphiphiles …

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 …

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.

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 …

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.

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 …

Theoretical Study Of H2o–Hf And H2o–Hcl: Comparison With Experiment, M. M. Szczesniak, Steve Scheiner, Y. Bouteiller

Chemistry and Biochemistry Faculty Publications

The H bonds in H₂O–HF and H₂O–HCl are studied and compared using ab initio molecular orbital methods and the results compared to experimental data. Basis sets used are: (i) triple valence 6‐311G∗∗ and (ii) double ζ with two sets of polarization functions. Electron correlation, included via second‐ and third‐order Møller–Plesset perturbation theory, is found to have profound effects on both systems, particularly H₂O–HCl. Both H bonds are strengthened substantially with a concomitant reduction in length. H‐bond energies and geometries calculated at correlated levels are in excellent accord with …

Ab Initio Study Of Fh–Ph3 And Clh–Ph3 Including The Effects Of Electron Correlation, Z. Latajka, Steve Scheiner

Chemistry and Biochemistry Faculty Publications

Ab initio calculations are carried out for FH–PH₃ and ClH–PH₃ using a basis set including two sets of polarization functions. Electron correlation is incorporated via Møller–Plesset perturbation theory to second and (in part) to third orders. The basis set is tested and found to produce satisfactory treatments of subsystem properties including geometries and dipole moments as well as the proton affinity and inversion barrier of PH₃. Electron correlation is observed to markedly enhance the interaction between PH₃ and the hydrogen halides. Its contribution to the complexation energy is 30% …