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Primary And Secondary Basis Set Superposition Error At The Scf And Mp2 Levels. H3n‐‐Li+ And H2o‐‐Li+, Z. Latajka, Steve Scheiner

Chemistry and Biochemistry Faculty Publications

The primary basis set superposition error (BSSE) results from the artificial lowering of the energy of each subunit of a pair by the presence of ‘‘ghost orbitals’’ of its partner. In addition, these ghost orbitals perturb the one‐electron properties of the molecule, causing a change in the interaction energy, an effect known as secondary BSSE which is not corrected by the counterpoise procedure. The primary and secondary BSSE are calculated for the interactions of NH₃ and H₂O with Li⁺, using a variety of different basis sets. It is found that the 2° BSSE can be …

Structure, Energetics, And Vibrational Spectrum Of H2o–Hcl, Z. Latajka, Steve Scheiner

Chemistry and Biochemistry Faculty Publications

H₂O–HCl is studied using a number of basis sets including 6‐31G∗∗ and variants which are augmented by a diffuse sp shell and a second set of d functions on O and Cl. Optimization of the geometry of the complex is carried out including explicitly electron correlation and counterpoise correction of the basis set superposition error (BSSE) at both the SCF and correlated levels. Correlation strengthens and shortens the H bond while BSSE correction leads to an opposite trend; these two effects are of different magnitude and hence cancel one another only partially. ΔH°(298 K) is …

A Mössbauer Effect Study Of The Structural And Magnetic Properties Of Y₂(Fe₁₋ₓalₓ)₁₄B, Ying-Chang Yang, Dwayne E. Tharp, Gary J. Long, Oran Allan Pringle, William Joseph James

Chemistry Faculty Research & Creative Works

The crystallographic and magnetic properties of Y₂(Fe₁₋ₓAlₓ)₁₄B, where x equals 0.00, 0.02, 0.04, 0.06, and 0.08, have been investigated by Mössbauer spectroscopy and magnetic measurements at room temperature and 85 K. Magnetic anisotropy and magnetization changes with aluminum substitution indicate that, because of size, the aluminum preferentially occupies the j₂ site over the remaining five crystallographically nonequivalent iron sites. This preferential occupation has been confirmed by Mössbauer spectral studies, which indicate that the compositional variation of the hyperfine field for each site is related to the number of near-neighbor aluminum atoms for the site. This compositional variation is helpful in …

Microemulsions, Lyotropic Liquid Crystals, And Other Association Structures, Jiafu Fang

Doctoral Dissertations

"Phase diagrams have been determined showing the extent of the inverse micellar or microemulsion region for several ionic surfactants and some cosurfactants. Hexylamine has been found to be a very effective cosurfactant giving rise to very good water solubilizing capacity at extremely low surfactant concentrations and very low cosurfactant levels at rather high initial hydrocarbon levels.

A fairly extensive study of phase equilibria of the system composed of sodium dodecyl sulfate, hexylamine, heptane, and water has been carried out. The conductivity behavior of the inverse micellar or microemulsion phase of the system shows the percolation phenomenon. Low angle X-ray diffraction …

Amphiphile Association Structures, Yun Yang

Doctoral Dissertations

"The amphiphile association behavior of Aerosol OT (sodium di-w-ethylhexylsulfoccinate) and p-xylene in combination with mixtures of different ratios of glycerol/water systems was studied and compared to that in the corresponding water and glycerol systems. The presence of glycerol strongly destabilized the inverse hexagonal liquid crystal phase observed in the aqueous system. The glycerol showed more ability to penetrate into the amphiphile bilayer than water in the lamellar liquid crystal phase. The influences of water and glycerol on the organization of amphiphile in the lamellar liquid crystal phase are of the same order.

The gross diffusion coefficient of 1% 2,4-diamino-6-piperidinopyrimidine-3-oxide in …

Interobserver Reliability In The Interpretation Of Computed Tomographic Scans Of Stroke Patients, David Shinar, Cynthia R. Gross, Daniel B. Hier, Louis R. Caplan, Jay P. Mohr, Thomas R. Price, Philip A. Wolf, Carlos S. Kase, Irene G. Fishman, Joshua A. Barwick, Selma C. Kunitz

Chemistry Faculty Research & Creative Works

Interobserver Reliability in Interpretation of Computed Tomographic Images Was Studied by Six Senior Neurologists Who Independently Evaluated on a Standardized Stroke Data Bank Form the Brain Lesions of 17 Patients. the Results Analyzed with K Statistics Yielded Moderate to Substantial Agreement on Most Items of Interest Including the Stroke Pathology and Anatomy. in General, the Levels of Agreement Were as High as Previously Reported for the Diagnosis of the Mechanism of the Stroke, and Much Higher Than on Many Stroke History Items and Items of Neurologic Examination. Excellent Agreement Was Obtained for the Detection of Infarcts and Intracerebral Hemorrhage, and …

Interaction Of Calcium With Hema/Maa Copolymers., Michael R. Van De Mark, N. D. Lian, M. Brandon, E. C. Eckstein

Chemistry Faculty Research & Creative Works

Polymeric materials based upon 2-hydroxyethyl methacrylate (HEMA) have been extensively used, especially in biomedical applications. Several reports have appeared in the literature during the past 20 years regarding the behavior of these materials upon exposure to body fluids. The results of these studies have ranged from good biocompatibility to calcification. The presence of methacrylic acid (MAA), in HEMA-based copolymers gives rise to a swelling transition at pH 7. The present study relates the swollen volume of HEMA/MAA gels to the concentrations of calcium salts at a pH where the MAA is ionized, as would occur for implanted gels. This swollen …

Lamellar Liquid Crystal And Other Phases In The System Sodium Dodecyl Sulfate, Hexylamine, Water, And Heptane, Jiafu Fang, Raymond L. Venable

Chemistry Faculty Research & Creative Works

Phase equilibria have been studied for the system composed of sodium dodecyl sulfate, hexylamine, heptane, and water. Greatest emphasis has been placed on the lamellar liquid crystal region and X-ray diffraction measurements. Equations are developed or modified to allow determination of the degree of penetration of water into the amphiphilic double layer as a function of water or amphiphile concentration. It is found that the interfacial area occupied by the polar or ionic head groups of amphiphiles increases with increasing water content. © 1987 Academic Press, Inc. All rights reserved.

Fourier Transform Nmr Self-Diffusion Studies Of A Nonaqueous Microemulsion System, K. P. Das, A. Ceglie, B. Lindman, Stig Friberg

Chemistry Faculty Research & Creative Works

Self-diffusion coefficients of the components of the microemulsion system glycerol/hexanol/sodium dodecyl sulfate (SDS) were determined in the presence and absence of an oil, p-xylene, and the results were compared with those from corresponding aqueous systems (i.e., glycerol replaced by water). In the aqueous system, the water in the hexanol rich isotropic liquid showed a diffusion coefficient less than 10% of that of free water, while that of hexanol was roughly 80% of that of free hexanol; such restricted motion of the water is consistent with the presence of water as discrete droplets. Partial substitution of p-xylene for hexanol did not …

Conductivity Study Of The Microemulsion System Sodium Dodecyl Sulfate-Hexylamine-Heptane-Water, Jiafu Fang, Raymond L. Venable

Chemistry Faculty Research & Creative Works

Conductivity measurements on this system are interpreted in terms of the percolation and effective medium theories. From this interpretation, the ratio of hexylamine to sodium dodecyl sulfate in the microemulsion droplet surfaces can be deduced. Following that determination, it is possible to obtain approximate values for the radius of the water pools and the number and surface area of droplets per unit volume of the microemulsion system. © 1987.

Phosphorus Levels And Disease On Lupins, J W. Bowden

Experimental Summaries - Plant Research

Trial 87LG39 (81LG29) 87ME62

Location: Pingaring.

It has been suggested that high levels of phosphorus application to lupins can reduce the impact of leaf and root diseases. Two old rotation trials provided a range of disease burdens, across which phosphate rates on lupins were applied. Disease scores, vegetative yields, phosphorus concentration and seed yields were measured.

(Details in Mark Sweetingham's report)

Residual Value Of Phosphate Fertilizers., M D A Bolland, M Baker, C. H. Phillips, D. Proudmore

Experimental Summaries - Plant Research

Trial 84M63

Residual value of phosphate fertilizers.

Location: South Carrabin Block of Merredin Research Station.

4th successive crop on new land. Trial has shown that the effectiveness of the different types of rock phosphate were about the fifth to one tenth as effective as the fresh (triple) superphosphate applied in 1984. The effectiveness of the superphosphate, decreased by 60 between year 1 and 2, and by a further 10-15% by 1987. This experiment will continue as pasture for 1988 and 1989, and will be re-cropped in 1990. The experiment is also assessing soil testing for P. but soil test data …

Barley Agronomy., K. J. Young

Experimental Summaries - Plant Research

Trial 87E6, 87MT45, 87SG11, 87ES8

Locations: Esperance Downs Research Station, Mount Barker Research Station, Salmon Gums Research Station, Melijinup Field Station,

Barley variety x time of planting

To study phenological development and its effect on yield in a range of barley cultivars at four planting dates.

Trial 87E42

Aphicide toxicology x barley variety.

Location: EDRS

To measure the effect of disulfoton (Disyston *R) applied as granules at seeding on barley, to determine if there is any phytotoxicity.

Trial 87ES40, 87E32

Barley variety x cereal aphids.

Location: Malijinup Field Station, Esperance Downs Research Station

To study the development of cereal aphids …

The Structure Of O-Antigen From Lipopolysaccharide Of Rhizobium Leguminosarum 128c53 And Its Nod-Fix-Mutant, Tong-Bin Chen

Masters Theses

The LPS of R. leguminosarum 128C53 sm^r rif^r (a streptomycin and rifampicin resistant strain of wild type 128C53) and its mutant ANU54 (nod^-, fix^-) were isolated from the bacterial pellet by hot phenol/water extraction followed by gel filtration chromatography. The O-antigen was isolated by mild-acid hydrolysis of the LPS and purified by gel filtration chromatography using a Sephadex G-50 or G-25. The following results were the same for both the parent and mutant. The composition and linkage of the O-antigen were determined by gas chromatography (GC), GC-mass spectrometry, ¹H and ¹³C nuclear …

Isolation And Partial Characterization Of Serogroup Specific Antigens From Bradyrhizobium Japonicum 61a123, Miguel Eduardo Carrion

Masters Theses

Serogroup specific antigens of Bradyrhizobium japonicum 61A123 were isolated using an immunochemical assay. Bacterial antigens were isolated by phenol-water extraction. These antigens were detected by inhibition of an enzyme linked immunosorbant assay (ELISA). Low pressure chromatography and digestion with proteinase K served to purify the antigens. Chemical composition was determined by gas chromatography (GC), mass spectrometry (MS), and colorimetric assays. The antigens were also characterized by sodium dodecyl sulfate (SDS)-polyacrylamide gel electrophoresis, and immunological properties determined by ELISA. These antigens were shown to be lipopolysaccharides (LPSs) containing fucose, a 2-amino-2,6-dideoxy hexose (unidentified), glucose and mannose as the major sugars, along …

Molecular Properties Of Cetiedil And Its Interactions With Human Erythrocytes, Chakravarthy Narasimhan

Dissertations

No abstract provided.

Structure Of L,L-Diphenylarsenanium Bromide Monohydrate, J. A. Campbell, R. Larsen, C. Campana, Sheldon E. Cremer, A. Gamliel

Chemistry Faculty Research and Publications

No abstract provided.

Measurement Of The Condensation Coefficient Of Water In The Umr Simulation Chamber, Daniel R. White, James L. Kassner, John C. Carstens, Donald E. Hagen, John L. Schmitt, Darryl J. Alofs, Alfred R. Hopkins, Max B. Trueblood, Max W. Alcorn, William L. Walker

Physics Faculty Research & Creative Works

The UMR Cloud Simulation Facility is described. The facility is designed to provide a controlled environment simulating the conditions of natural atmospheric processes. It consists of two cooled-wall expansion cloud chambers and peripheral instrumentation for generation and characterization of aerosols used for cloud formation studies. Results of initial studies of the growth of warm cloud droplets and inferred measurements of the condensation coefficient are described.

The Synthesis And Characterization Of Polycarbonates Based On 1,1'-Dihydroxyethyl-2,2'-Biimidazole, Judith J. Garces

Masters Theses

"The synthesis of polycarbonates formed by the reaction of 1,1'-dihydroxyethyl-2,2'-biimidazole and diphenyl or diethyl carbonates was investigated and the products formed were characterized. The molecular weights of the polymers were dependent on catalyst, ratio of starting materials, nature of carbonate (aromatic or aliphatic) and method of polymerization. Isolated polymers exhibit a linear structure. They have no well-defined melting points (melting pt. range of 280- 330⁰C) indicating low degree of crystallization, and undergo less than 9% decomposition below 200⁰C"--Abstract, page ii.

Synthesis And Characterization Of Some Sf₅- Containing Sulfonic Acids, Robert J. Willenbring

Dissertations and Theses

Pentafluorosulfur (VI) bromide (SF₅Br) adds to olefins of the form CX₂=CX₂, where X= H or F, with the pentafluorosulfur group usually adding to the carbon with more hydrogens attached to it. This series of compounds was used in an attempt to prepare the corresponding sulfonic acid hydrates of the general formula SF₅CX₂CX₂SO₃H·nH₂O, in order to have these compounds tested as possible fuel cell electrolytes. The reaction scheme involved reflux of the SF₅Br adduct with an equimolar amount of sodium sulfite in 50% …

The Synthesis Of (3s, 8as) 3-(2-Phenyl-2-Propyl-)-1-Oxo-Octahydro-2h-Pyrido[1, 2a] Pyrazine As A Model Compound To Test Proposed Structure-Activity Relationships And Metabolism Of The Natural Mycotoxin And Muscle Relaxant: Verruculotoxin, Karen Earlene Couch

Dissertations and Theses @ UNI

The compound verruculotoxin, a natural mycotoxin, was isolated in 1974 and found to be biologically active, having anesthetic properties. Two theories have been proposed to explain the biological activity of verruculotoxin. The first theory states that verruculotoxin is not the biologically active compound, but, rather, as a result of metabolism in the body, a biologically active metabolite is produced. The second theory states that the biological activity of verruculotoxin is dependent upon the molecules ability to mimick various co-formations with respect to the spatial arrangement of the aromatic ring and nitrogen atom. These theories are used to explain the activity …

Structure Of L-Benzyl-2,2,3,3-Tetramethyl-L-Phenylphosphetanium Bromide, A Cyelobutane Derivative, J. A. Campbell, R. Larsen, C. Campana, Sheldon E. Cremer

Chemistry Faculty Research and Publications

No abstract provided.

Surfactants And The Stratum Corneum Lipids, Stig E. Friberg, Lisa Goldsmith, Hamdan Suhaimi, Linda D. Rhein

Chemistry Faculty Research & Creative Works

A simplified mixture of model stratum corneum lipids was mixed with different surfactants to make a preliminary estimation of the influence of surfactants on the stratum corneum lipid structure. The results revealed differences between cationic and anionic surfactants and between anionic surfactants with different structures. © 1998.

Foams From Aqueous Systems Of Polymerizable Surfactants, Stig Friberg, Jia Hwa Fang

Chemistry Faculty Research & Creative Works

Polymerization was made in aqueous foams stabilized by a combination of a polymerizable surfactant, sodium (ω)-acrylamidoundecanoate (NaAAU), and oleyl alcohol. The common two-phase foams stabilized by a monomolecular layer of surfactant were not sufficiently stable to allow polymerization in foamed form, nor were such foams obtained in the two-phase region of aqueous solution and the liquid crystalline phase of hexagonally packed cylinders. Sufficient foam stability was found first when the lamellar liquid crystal formed by the combination of oleyl alcohol, the NaAAU, and the water. These foams were polymerized and shown to retain the liquid crystalline structure after polymerization. © …

Critical Phenomena In Nonaqueous Microemulsions, Stig Friberg, Yuh Chirn Liang

Chemistry Faculty Research & Creative Works

The pseudo ternary phase diagrams of the four-component system glycerol, sodium dodecyl sulfate, hexanol and decane with the weight ratio of hexanol to decane equal to 100/0, 90/10, 75/25, 50/50, and 25/75 were determined at 30°C. The systems gave only isotropic solutions and no liquid crystalline phases. The nonaqueous regions corresponding to the W/O microemulsion region in aqueous systems suggested critical behavior as demonstrated by the convergence of tie lines and by light scattering intensity which gave a pronounced maximum at the point of converging tie lines. This maximum was transferred to higher glycerol/hexanol ratios with added surfactant and to …

The Mechanism By Which Oxygen And Cytochrome C Increase The Rate Of Electron Transfer From Cytochrome A To Cytochrome A3 Of Cytochrome C Oxidase, D. Bickar, J. F. Turrens, A. L. Lehninger

Chemistry: Faculty Publications

When cytochrome c oxidase is isolated from mitochondria, the purified enzyme requires both cytochrome c and O2 to achieve its maximum rate of internal electron transfer from cytochrome a to cytochrome a3. When reductants other than cytochrome c are used, the rate of internal electron transfer is very slow. In this paper we offer an explanation for the slow reduction of cytochrome a3 when reductants other than cytochrome c are used and for the apparent allosteric effects of cytochrome c and O2. Our model is based on the conventional understanding of cytochrome oxidase mechanism (i.e. electron transfer from cytochrome a/Cu(A) …

The Homeo Domain Of A Murine Protein Binds 5' To Its Own Homeo Box., Abraham Fainsod, Leonard D. Bogarad, Tarmo Ruusala, Martin Lubin

Dartmouth Scholarship

Nuclear protein extracts from day 12.5 mouse embryos were used to study protein binding to DNA sequences 5' of the Hox 1.5 homeo box. Embryos of this developmental stage are known to express this gene. DNA binding protein blotting and retardation gel techniques show that murine embryonic nuclear proteins specifically bind a 753-base pair (bp) DNA fragment from the region upstream of the Hox 1.5 homeo box. A fusion protein containing the Hox 1.5 homeo domain constructed in lambda gt11 also binds the same 753-bp DNA fragment. Specific binding of the fusion protein to the upstream DNA fragment shows that …

High Performance Liquid Chromatographic Determination Of Thromboxane B2 In Human Serum As A Methoxime-Panacyl Ester Derivative, Robert H. Pullen

Masters Theses

No abstract provided.

Assignment Of The Lattice Modes In Tcnq0 Single Crystals, K.M. White, K.-H. Brose, Craig J. Eckhardt

Craig J. Eckhardt Publications

A complete assignment of the six librational modes of the TCNQ⁰ crystal has been made employing both polarized Raman spectroscopic measurements and lattice dynamical calculations. Agreement between theory and experiment is good and modes at 40.5, 74.5, and 96 cm^-1 are assigned as A_g active and those at 63, 75.5, and 104 cm^-1 are B_g active. The lattice modes are found to be clearly separated from the molecular modes. The study emphasizes the importance of crystal optics and quality in the measurement of the polarized Raman spectra of biaxial crystals. The Journal of Chemical Physics …

Charge Transfer-Oxy Radical Mechanism For Anti-Cancer Agents, Peter Kovacic, James R. Ames, Paavo Lumme, Hannu Elo, O. Cox, Michael D. Ryan

Chemistry Faculty Research and Publications

The proposal is advanced that anti-cancer drugs generally function by charge transfer resulting in formation of toxic oxy radicals which destroy the neoplasm. Electrochemical studies were performed with some of the main types of agents: iminium ions (adenine iminium from alkylating species, iminium metabolite of 6-mercaptopurine, nitidine, other polynuclear iminiums) and metal complexes (Pt(II)diaquodiammine-guanosine, copper salicylaldoximes). Reduction potentials ranged from -0.4 to -1.2 V. Literature data for quinones are presented and radiation is discussed. Based on the theoretical framework, a rationale is offered for the carcinogen-anti-cancer paradox and the role of antioxidants.