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Molecular Dynamics In Hydrogen‐Bonded Interactions: A Preliminary Experimentally Determined Harmonic Stretching Force Field For Hcn‐‐‐Hf, B. A. Wofford, Shannon Lieb, J. W. Bevan

Scholarship and Professional Work - LAS

Observation of the 2ν₁ overtone band in the hydrogen‐bonded complex HCN‐‐‐HF permits evaluation of the anharmonicity constant X _{1 1}=−116.9(1) cm^{− 1} and determination of the anharmonicity corrected fundamental frequency ω₁. This information, and available data from previous rovibrational analyses in the common and perdeuterated isotopic species of HCN‐‐‐HF, offer an opportunity for calculation of an approximate stretching harmonic force field. With the assumptions f _{1 2}=f _{2 4}=0.0, the remaining force constants (in mdyn/Å) are evaluated as: f _{1 1}=8.600(20), f _{2 2}=6.228(9), f _{3 3}=19.115(40), f _{4 …}

Improved Synthesis Of 5-Methylbenz(A)Anthracene, Jia Che, Dominic T.C. Yang

Journal of the Arkansas Academy of Science

A revised synthesis of 5-methylbenz(a)anthracene is reported. It involves only three simple and convenient steps starting from a commercially available compound, and gives a 82% overall yield. Bromination of 5-methylbenz(a)anthracene with N-bromosuccinimide (NBS) in carbon tetrachloride furnishes 5-bromomethylbenz(a)anthracene in a 92% yield. When bromination is carried out using dimethylformamide as the solvent, 7-bromo-5-methylbenz(a)anthracene is formed as the exclusive product.

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.

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.

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 …

Preparation Of Geminal Diflourodienes, Antonio Landavazo

Retrospective Theses and Dissertations

This report discusses research involving the preparation of germinal difluorodienes. Free radical addition of dibromodifluoromethane to 1-hexene and cyclohexene was performed, followed by a double dehydrohalogenation to yield 1,1-difluoro-1,3-heptadiene and 3-(difluoromethylene)cyclohexene, respectively. NMR, IR, and mass spectral data were obtained and presented as groundwork for further research. A study comparing the free radical initiators, benzoyl peroxide and 2,2’-azobis-(2-methyl)proprionitrile (AIBN) was included, showing neither as ideal initiators for the free radical additions performed. The relative stabilities of the bromodifluoromethyl and the difluoroiodomethyl radicals were approximated. A Diels-Alder reaction of 1,1-difluoro-1,3-heptadiene with 4-phenyl-1,2,4-triazoline-3,5-dione produced the expected [4 + 2] cycloadduct in good …

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 …

Reversible Oxygenation Of Oxygen Transport Proteins, Charles Michael Drain, Barry B. Cordon

Publications and Research

A lecture demonstration illustrating changes in the visible spectra of oxygen transport proteins upon reversihle oxygen binding is reported. The coloration upon exposure to oxygen is dramatic. Deoxyhemoglobin changes from purple to red, deoxyhemocyanin is transformed from colorless to blue, while colorless deoxyhemerythrin turns red. This demonstration illustrates an interesting example of a chemically reversible reaction and is used in the discussion of basic thermodynamic properties. A comparison of the physical characteristics of these oxveen storaee and transn.o rt ~ro- A teins is provided to illustrate the stru&ral diversity associated with these proteins having a similar biological role.

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 …

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

Dissertations

No abstract provided.

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 …

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 …

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 …

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) …

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.

Ua66/7/2 Hilltopper News, Wku Chemistry

WKU Administration Documents

Newsletter created by and about the WKU Chemistry department.

The Synthesis And Evaluation Of The Cardiovascular Activity Of Novel Imidazole Ring Systems, Joseph E. De Los Angeles

Chemistry & Biochemistry Theses & Dissertations

An investigation was undertaken to synthesize and evaluate the cardiovascular activity of two imidazole ring systems. Imidazoles with hypotensive activity would provide novel potential antihypertensive drugs. These novel structures may also find use as chemical probes in the study of the cardiovascular system and as prototypes for other potential cardiovascular agents.

The histamine derivative, 7,7-dipyridyl-4,5,6,7-tetrahydroimidazo-[4,5-c]pyridine (ligand l), was demonstrated to possess significant hypotensive activity in laboratory rats. A 15 mg/Kg dose of ligand 1 produces a statistically significant decrease in blood pressure when injected IP. This hypotensive effect is also associated with marked increase in heart rate. Although compound 1 …

The Esterases Of The Galleria Mellonella Larvae, Salmah Juraimi

Masters Theses & Specialist Projects

Some properties of esterases of the greater wax moth larvae, Galleria mellonella (L.) were examined and the enzyme partially purified. Tris buffer was chosen as the buffer system over veronal buffer. The former causes less hydrolysis of the acetylsalicylic acid. Esterase activities were determined with acetylasalicylic acid in tris buffer (00.05 M, pH 7.85 with 0.1 M EDTA) and with acetyl-p-hydroxybenzoic acid in the same buffer. The enzyme was partially purified by combination of acetone powder preparation, ammonium sulfate precipitation, ion-exchange chromatography, and gel filtration.

The starting enzyme preparation was obtained from aceton powder preparation. The ratio of esterase activity …

Reactive Counterion Surfactant Catalysis Of Hydroxamic Acid Hydrolysis With Perfluorooctanoic Acid, Mohamed El-Sayed Ayoub

Masters Theses

A micellar effect upon the rate of hydrolysis of hydroxamic acids in aqueous perfluorooctanoic acid has been demonstrated for hydroxamic acids with chain lengths of six , eight, and ten carbons. In this system the counterion, hydrogenion, is a catalyst. Typical rate constant-surfactant concentration profiles for micellar catalysis were obtained. The results for these hydrolyses are consistent with the pseudo-phase model for micellar effects.

In addition the Arrhenius activation energies were determined for the reaction of octanohydroxamic acid at surfactant concentrations above and below the critical micelle concentration of the surfactant. The activation energy is lower for reaction in the …

Identification Of Fibroblasts As A Major Site Of Albumin Catabolism In Peripheral Tissues, Jeffrey L. Strobel, Susan G. Cady, Thomas K. Borg, Louis Terracio, John W. Baynes, Suzanne R. Thorpe

Faculty Publications

Rat serum albumin has been labeledw ith dilactitollZ5I- tyramine,( 12‘I-DLT) a radioactive tracer which remains entrappedw ithin lysosomes following cellular uptake and degradation of the carrier protein. Similar kinetics of clearance from the rat circulation were observed for albumin labeled conventionally with lZsI or 12‘I-DLT-albumin, both proteinhsa ving circulating half-lives of -2.2 days. In contrast, the recovery of whole body radioactivity had half-lives of -2.2 and 5.1 days, respectively, for the two protein preparations, indicating substantial retention of degradation products derived from catabolism of ”‘I-DLT-albumin. Measurement of total and acid-soluble radioactivity in tissues 2 or 4 days after injection of …

Mössbauer Spectroscopic Studies Of Hemoglobin And Its Isolated Subunits, G. R. Hoy, D. C. Cook, R. L. Berger, F. K. Friedman

Physics Faculty Publications

Samples of 90% enriched ⁵⁷Fe hemoglobin and its isolated subunits have been prepared. Mössbauer spectroscopic measurements have been made on three such samples. Sample one contained contributions of oxyhemoglobin, deoxyhemoglobin, and carbonmonoxyhemoglobin. This sample was studied from a temperature of 90 K down to 230 mK. Measurements were also made at 4.2 K using a small applied magnetic field of 1.0 T. In general, the measured quadrupole splittings and isomer shifts for each component agreed with previous measurements on single component samples in the literature, and thus demonstrated that chemically enriched hemoglobin has not been altered. The second and …

Identification Of N Epsilon-Carboxymethyllysine As A Degradation Product Of Fructoselysine In Glycated Protein, Mahtab U. Ahmed, Suzanne R. Thorpe, John W. Baynes

Faculty Publications

The chemistry of Maillard or browning reactionosf glycated proteins was studied using the model compound, Nu-formyl-W-fructoselysine(f FL), an analog of glycated lysine residues in protein. Incubation of fFL (15 mM) at physiological pH and temperature in 0.2 M phosphate buffer resulted in formation of lVcarboxymethyllysine (CML) in about 40% yield after 15 days. CML was formed by oxidative cleavage of fFL between C-2 and C-3 of the carbohydrate chain and erythronic acid (EA) was identified a s , the split product formed in the reaction. Neither CML nor EA was formed from fFL under a nitrogen atmosphere. The rate of …

Magnesium, Copper And Zinc Concentrations In Blood From Children With Diabetes Mellitus, Linda Lowers Jenkins

Chemistry & Biochemistry Theses & Dissertations

Trace element levels in blood from diabetic children were investigated and compared to control children. Plasma, erythrocyte, mononuclear and polymorphonuclear cells were analyzed for magnesium, copper, and zinc content. Leukocyte separation was performed by density gradient centrifugation on Ficoll-Hypaque, followed by washing steps to remove platelet contamination and hypotonic lysis to remove red cell contamination. Polarized Zeeman-effect atomic absorption spectroscopy was used for trace metal analysis.

Decreased plasma magnesium levels were observed in the diabetic children. This finding is well documented and probably due to increased urinary magnesium loss from glycosuria. Lymphocyte magnesium levels in the diabetic children were also …

Mutual Orientation Effects On Electron-Transfer Reactions Between Porphyrins, Robert J. Cave, Paul Siders, R.A. Marcus

All HMC Faculty Publications and Research

Mutual orientation effects on the rate of nonadiabatic electron transfer between several diporphyrin pairs of experimental interest are examined. The electronic matrix element for electron transfer is calculated within a one-electron spheroidal model for a variety of states and orientations which are relevant to both biological and synthetic electron-transfer systems. Both the mutual orientation of the pairs and the nodal structure of the donor and acceptor orbitals can have large effects on calculated rates.

Biomarker Geochemistry Of The Miocene Monterey Formation, West San Joaquin Basin, California: Implications For Petroleum Generation, Michael A. Kruge

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

Much of the Miocene Monterey Formation of California is rich in biogenic sediment, especially organic matter and silica. Because of the geologic structure, the Monterey in the subsurface near Lost Hills in the San Joaquin Basin forms a natural laboratory for the study of the diagenetic responses of these materials. Rocks of similar age and lithology are buried to depths ranging between 500 and 3500 m, and are thus exposed to a temperature range of 45–130°C. The diagenetic progression of silica from opal-A to opal-CT to microquartz is well-documented in Monterey burial history studies. However, diagenetic indicators need to be …

Electrochemistry Of Dihalogenated Nicotonic Acids In Aqueous And Aprotic Media, Ali U. Shaikh, Tappi A. Dixon, Lourie A. Battles, Frank L. Setliff

Journal of the Arkansas Academy of Science

The electrochemical reduction of several 2,5- and 5,6- dihalonicotinic acids have been studied in dimethyl sulfoxide as well as in aqueous buffers of different pH. The polarographic half-wave potentials for the reduction of these compounds in both media are reported here. The compounds appear to reduce at the carboxyl group. The presence of halogen atoms on the pyridine ring facilitates reduction.

Electrochemical Investigation Of The Effects Of Temperature, Ph, And Electrolyte On The Electron Transfer Reactions Of Cytochrome C, Kent Brian Koller

Theses and Dissertations

Spectroelectrochemical and electrochemical methods have been used to investigate the characteristics of heterogeneous electron transfer between cytochrome c and indium oxide electrodes. Direct electron transfer between cytochrome c and solid electrodes is of interest due to the interfacial character of electron transfer between the protein and its membrane-bound physiological redox partners. The conformation of ferricytochrome c is affected more by changes in temperature or pH than is its reduced form, ferrocytochrome c. This difference in conformational stability is attributed to the +1 charge of the heme in ferricytochrome c that is largely embedded in the hydrophobic interior of the enzyme. …

Characterization Of The Capsular Polysaccharides On Cell Membranes Of Rhizobium Trifolii And Three Of Its Nod- Mutants, Jesse Ardosa

Masters Theses

The ever-present specter of the inavailability of food production to increase in direct proportion to population growth haunts practically every nation of the world. As more and more tracts of land are incorporated to accommodate expanding cities, they become less available for food production. Emphasis, therefore, is placed on obtaining a higher yield per acreage planted. Since fertilization is not reliable in the long term due to an eventual depletion of raw materials for fertilizers, the ability of plants like legumes to assimilate free soil nitrogen on their own has become increasingly important [1,11,14,17]. However, the mechanisms involved are still …

Use Of Isomerizable N-Alkylmerocyanine Dyes To Robe Molecular Interactions Within Micellar Solubilization Sites, Kim Jason Dennis

University of the Pacific Theses and Dissertations

Effects of aqueous surfactant solutions upon cis/trans isomerization reactions of various N-alkyl-merocyanine dyes (II) were studied. Dramatic rate enhancements were found for all dyes in CTAB and SDS solutions above the CMC. CTAB solutions showed the greatest effect with some dye isomerizations catalyzed in excess of 1000-fold. Increases in either CTAB concentration or dye isomerization rates. N-methyl through N-pentyl dye isomerization rates were measured as a function of CTAB concentration and the data treated according to the pseudophase model for micellar catalysis. K_S values ranged from 198 to 2000 M^-1 for N-methyl to N-pentyl dyes, respectively. Micellar rate …

Amphiphilic Association Structures And Some Aspects Of Foam Stability, Jia-Hwa Fang

Doctoral Dissertations

"This investigation was performed in order to study two interesting and important problems in foams.

Foam separation was studied in the model system of water - sodium octylsulfonate - decanol. The efficiency of foam separation as a function of surfactant concentration and decanol content were measured. The results were related to the association structures of amphiphiles in aqueous systems.

Foam polymerization was conducted in the amphiphilic system containing water, polymerizable surfactant and oleyl alcohol. Liquid foams were produced in one three - phase region. The location and optical pattern of liquid crystals on the foam surface were observed by photomicroscope …