Chemistry Commons^™

Vapor–Liquid Coexistence Of Quasi-Two-Dimensional Stockmayer Fluids, G.T. Gao, Xiao Cheng Zeng, Wenchuan Wang

Xiao Cheng Zeng Publications

A quasi-two-dimensional (2D) Stockmayer model is developed in which the center of mass of the molecule is confined on a plane while the dipole of the molecule can rotate freely in three dimensional space. This model entails essential characteristics of systems such as dipolar molecules physisorbed on a solid surface, or a Langmuir monolayer consisting of short-chain molecules with a dipolar tail. The Gibbs ensemble Monte Carlo technique is employed to determine the vapor– liquid equilibria of the model fluids. An Ewald sum for this quasi-2D model is formulated to account for the long-range dipolar interactions. Three systems with different …

The Hydroperoxyl Radical Dimer: Triplet Ring Or Singlet String?, Justin T. Fermann, Brian C. Huffman, Gregory S. Tschumper, Henry F. Schaefer

Chemistry Faculty Research & Creative Works

In order to determine the lowest energy isomer of the hydroperoxyl radical dimer, H2O4, ab initio quantum mechanical methods were employed to predict the geometrical structures, relative energies, harmonic vibrational frequencies, and associated IR intensities of both open chain and cyclic isomers. Two minima were located on the open chain potential energy surface, one of C2 symmetry and one of C1 symmetry. The relative energies of the different H₂O₄ structures vary strongly with level of theory. The most reliable treatment used in the present study predicted that the global minimum is the closed-shell C1 chain isomer which …

Partitioning Of The Reactive Nitrogen Reservoir In The Lower Sratosphere Of The Southern Hemisphere: Observations And Modeling, R. S. Gao, D. W. Fahey, R. J. Salawitch, S. A. Lloyd, D. E. Anderson, R. Demajistre, C. T. Mcelroy, E. L. Woodbridge, R. C. Wamsley, S. G. Donnelly, L. A. Del Negro, M. H. Proffitt, R. M. Stimpfle, D. W. Kohn, S. R. Kawa, L. R. Lait, M. Loewenstein, J. R. Podolske, E. R. Keim, J. E. Dye, J. C. Wilson, K. R. Chan

Chemistry Faculty Publications

Measurements of nitric oxide (NO), nitrogen dioxide (NO2), and total reactive nitrogen (NOy = NO + NO2 + NO3 + HNO3 + ClONO2 + 2N2O5 + ...) were made during austral fall, winter, and spring 1994 as part of the NASA Airborne Southern Hemisphere Ozone Experiment/Measurements for Assessing the Effects of Stratospheric Aircraft mission. Comparisons between measured NO2 values and those calculated using a steady state (SS) approximation are presented for flights at mid and high latitudes. The SS results agree with the measurements to within 8%, suggesting that the kinetic rate coefficients and calculated NO2 photolysis rate used in …

Reactions Of Hydroxylamine With Metal Porphyrins, In Kyu Choi, Yanming Liu, Zhongcheng Wei, Michael D. Ryan

Chemistry Faculty Research and Publications

The reaction of hydroxylamine with a series of metal porphyrins was examined in methanol/chloroform media. The reductive nitrosylation reaction was observed for the manganese and iron porphyrins, leading to a nitrosyl complex that precipitated out of the solution in good isolatable yield (80−90%). This reaction could be used synthetically for the generation of iron and manganese porphyrin nitrosyl complexes and was particularly useful for making isotopically labeled nitrosyl complexes. On the other hand, Co^II(TPP) and Cr(TPP)(Cl) did not react with hydroxylamine under anaerobic conditions. With trace amounts of oxygen, the reaction of Co^II(TPP) with hydroxylamine led …

Quantitation Of Ethidium-Stained Closed Circular Dna In Agarose Gels, Michael F. Shubsda, Jerry Goodisman, James C. Dabrowiak

Chemistry - All Scholarship

The fluorescence of ethidium bromide (EB) bound to equimolar amounts of supercoiled form I and unstrained linear form III pBR322, SV40 and PM2 DNA in agarose gels has been measured by scanning a photographic negative of the gel with a microdensitometer. For SV40 and PM2 DNA, commonly used staining conditions cause both forms, i.e. linear and supercoiled, to fluoresce to the same extent. This obviates the need to use a correction factor for the fluorescence of form I DNA when measuring the amount of this form relative to the amounts of unstrained forms in agarose gels. In the case of …

Monte Carlo Simulation Of The Solid To Superliquid Phase Transition Of Langmuir Monolayers. Ii. Characteristics Of Phase Transition, M.D. Gibson, D.R. Swanson, Craig J. Eckhardt, Xiao Cheng Zeng

Craig J. Eckhardt Publications

The restricted-to-free rotator phase transition of fatty acid monolayers has been modeled using a potential which represents the amphiphiles as planar cross sections of fourfold symmetry. Using much larger system sizes than paper I [D. R. Swanson, R. J. Hardy, and C. J. Eckhardt, J. Chem. Phys. 99, 8194 (1993)], Monte Carlo simulations of the isobaric–isothermal ensemble of model systems with varied number of objects were undertaken to study the effect of system size on the characteristics and order of the phase transition. A peak in the specific heat vs temperature curve was observed near the transition. For each system …

Conformations And Relative Stabilities Of The Cis And Trans Isomers In A Series Of Isolated N-Phenylamides, V. P. Manea, K. J. Wilson, John R. Cable

Chemistry Faculty Publications

The gas-phase conformations of a series of isolated N-phenylamides have been determined from vibrationally resolved electronic spectra obtained by resonant two-photon ionization in a supersonic jet expansion. Both the cis and trans isomers of formanilide were identified, with the cis isomer in 6.5% abundance. The spectral features displayed by this isomer are consistent with a nonplanar geometry which undergoes a large change in the phenyl torsional angle following electronic excitation. The more abundant trans isomer of formanilide adopts a planar structure and is stabilized by 2.5 kcal/mol with respect to the cis isomer. In the excited electronic state the relative …

Oxidized Sterols In Patients With Diabetic Heart Disease And Microwave-Mediated Stereoselective Synthesis Of 3-Keto Cholesterol And Cholesterol Epoxide, Cholesteryl Ester Epoxides, Meenakashi N. Kothavale

Theses

Oxidized low density lipoproteins (ox-LDL) may play important role in mediating hypercholesterolemic endothelial dysfunction. The uptake of modified LDL by macrophages to form foam cells has been implicated in the enhancement of atherosclerosis. Recent reports have suggested that when LDL undergoes oxidation in vitro , it is accompanied by a substantial loss of free and esterified cholesterol leading to the formation of oxidation products of cholesterol ( oxysterols). These compounds are present in human atherosclerotic plaques and in human foam cells.

In this regard we have recently studied the plasma sterol composition in diabetic heart patients We have found cholesterol …

Catalytic Control Of Nitric Oxide With Gaseous Or Solid Reducing Materials, Xiaoyong Tang

Theses

Air pollution from mobile sources is an increasingly serious problem throughout most of the industrialized would. Diesel powered vehicles, because of their higher thermal efficiency, tend to emit less carbon monoxide and unburned hydrocarbons than gasoline vehicles, but emit significant quantities of NO_x. Therefore, it is essential to develop improved emission control equipment in diesel engines. A fixed bed catalytic reactor was used to study the decomposition of NO and the reduction of NO to N₂ by different reductants that can be found in diesel exhaust, such as hydrocarbons, CO and elemental carbon over different catalysts. The …

Chiral Separation Of Monoterpenes Using Mixtures Of Sulfated Β-Cyclodextrins And Α-Cyclodextrin As Chiral Additives In The Reversed-Polarity Capillary Electrophoresis Mode, Kyung Hyun Gahm, Lisa W. Chang, Daniel W. Armstrong

Chemistry Faculty Research & Creative Works

The use of mixtures of sulfated β-cyclodextrins and native α-cyclodextrin as chiral additives in capillary electrophoresis was evaluated for the chiral resolution of neutral, cyclic and bicyclic monoterpenes, including α-pinene, (β-pinene, camphene and limonene. Binding properties of sulfated β-cyclodextrins towards these monoterpenes were studied. It was found that there was no enantioresolution of these terpenoids over the concentration range studied. However, the addition of α-cyclodextrin to the running electrolyte in addition to 6.5 mM sulfated β-cyclodextrins, imparted differences in the mobilities of the terpenoid enantiomers and resulted in remarkable enantiomeric separations of α-pinene (R(s)=25), β-pinene (R(s)=12), camphene (R(s)=12) and limonene …

Nucleotide Or Nucleoside Photoaffinity Compound Modified Antibodies, Methods For Their Manufacture And Use Thereof As Diagnostics And Therapeutics, Boyd E. Haley, Heinz Köhler, Krishnan Rajagopalan, Gabriela Pavlinkova

Chemistry Faculty Patents

Sites on antibodies having affinity for photoaffinity compounds, in particular purine or azidopurine containing compounds are taught. These sites provide for the site-specific attachment of nucleotide photoaffinity compounds to antibodies, e.g., ATP- or GTP-analog photoaffinity compounds by photochemical reaction. These nucleotide photoaffinity compounds may additionally be attached to molecules having a desired therapeutic or diagnostic activity, and the resultant conjugates used as diagnostics or therapeutics.

Enhancing The Performance Of Membrane Introduction Mass Spectrometry By Organic Carrier And Liquid Chromatographic Separation, Shi Ouyang, Yong Hong Chen, Yan Xu

Chemistry Faculty Publications

A method of membrane introduction mass spectrometry with liquid chromatographic separation (LC/MIMS) for the analysis of volatile organic compounds (VOCs) in water has been developed. The method not only inherited all the advantages of membrane introduction mass spectrometry by flow-injection analysis (FIA/MIMS), but also expanded the application of MIMS to the determination of compounds with identical quantitation ions. Because the quantitation by LC/MIMS is based on two-dimensional identification (retention time (tr) and mass-to-charge ratio ()), it provides a tangible approach to the analysis of VOCs in complex aqueous samples. In this work, a C18 column and a mobile phase (methanol/water) …

Synthetic Strategies For The Construction Of Enantiomeric Azanoradamantanes, Daniel Becker, Roger Nosal, Daniel L. Zabrowski, Daniel Flynn

Chemistry: Faculty Publications and Other Works

The amino azanoradamantane hexahydro-2,5b-methano-IH-3aS,3aa,6aa-cyclopenta-[clpyrrole-4a-amine 1and the corresponding enantiomer ent-1 have been prepared along with benzamide derivatives SC-52491and SC-52490, respectively, which are of pharmaceutical interest. The key meso-azabicyclo[3.3.0] intermediate 3 was prepared via three separate routes: a [3+2] cycloaddition route, a radical cyclization/ionic cyclization route, and a reductive Pauson-Khand route.

Identification Of The Adp-L-Glycero-D-Manno-Heptose-6-Epimerase (Rfad) And Heptosyltransferase Ii (Rfaf) Biosynthesis Genes From Nontypeable Haemophilus Influenzae 2019, W A. Nichols, B W. Gibson, William Melaugh, N G. Lee, M Sunshine, M A. Apicella

Chemistry Faculty Publications

Haemophilus influenzae is an important human pathogen. The lipooligosaccharide (LOS) of H. influenzae has been implicated as a virulence determinant. To better understand the assembly of LOS in nontypeable H. influenzae (NtHi), we have cloned and characterized the rfaD and rfaF genes of NtHi 2019, which encode the ADP-L-glycero-D-manno-heptose-6-epimerase and heptosyltransferase II enzymes, respectively. This cloning was accomplished by the complementation of Salmonella typhimurium lipopolysaccharide (LPS) biosynthesis gene mutants. These deep rough mutants are novobiocin susceptible until complemented with the appropriate gene. In this manner, we are able to use novobiocin resistance to select for specific NtHi LOS inner core …

Characterization Of A Transposon Tn916-Generated Mutant Of Haemophilus Ducreyi 35000 Defective In Lipooligosaccharide Biosynthesis, B W. Gibson, A A. Campagnari, William Melaugh, M A. Apicella, S Grass, Jing Wang, Katherine L. Palmer, R S. Munson

Chemistry Faculty Publications

To define the role of the surface lipooligosaccharide (LOS) of Haemophilus ducreyi in the pathogenesis of chancroid, Tn916 mutants of H. ducreyi 35000 defective in expression of the murine monoclonal antibody (MAb) 3F11 epitope on H. ducreyi LOS were identified by immunologic screening. One mutant, designated 1381, has an LOS which lacks the MAb 3F11 epitope and migrates with an increased mobility on sodium dodecyl sulfate-polyacrylamide gel electrophoresis. The gene disrupted by the Tn916 element in strain 1381 was identified by cloning the sequences flanking the Tn916 element. The sequences were then used to probe a lambda DASHII genomic library. …

An Approach To A Generalized Synthesis For 2-Halo-1,1-Diarylalkenes, Cheryll R. Roberts

Theses, Dissertations and Capstones

This study was concerned with the development of a generalized synthesis of halogenated 1,1-diarylalkenes. The alkylation of 1,1-diphenylethylene was carried out by the addition of organolithium compounds (C Li, PhLi, t-BuLi, n-BuLi). N-bromo-succinimide (NBS) was used for bromination. The reaction forming triphenylbromo-ethylene gave the largest percent yield (93.6%). The reaction forming 2-bromo-3,3- dimethyl-l,l-dipheny1-1-butene resulted in a 38.1% yield. Each product structure was confirmed by proton and carbon-13 nuclear magnetic resonance, and infrared spectroscopy.

Determination Of Selected Hydrocarbon Concentrations In Reformate Using Near Infrared Spectroscopy, Roy Roger Bledsoe Jr.

Theses, Dissertations and Capstones

Near infrared spectroscopy was used as a quantitative technique employing multiple linear regression and partial least squares regression for determining the concentration of hydrocarbon groups and individual hydrocarbons present in reformate, a refinery process stream. Models were generated for total aromatics, benzene, toluene, total xylenes and individual xylene isomers, ethylbenzene, total paraffins, n-hexane, n-heptane, total isoparaffins, isopentane, 2-methylhexane, total naphthenes, methylcyclopentane, and total olefins. Some models are being used with an on-line instrument to constantly monitor a reformate stream as it leaves the reforming unit, with a standard error of performance of 0.118 volume percent for the prediction …

Directed Panspermia. 3. Strategies And Motivations For Seeding Star-Forming Clouds, Michael Noah Mautner

Chemistry Publications

Microbial swarms aimed at star-forming regions of interstellar clouds can seed stellar associations of 10 - 100 young planetary systems. Swarms of millimeter size, milligram packets can be launched by 35 cm solar sails at 5E-4 c, to penetrate interstellar clouds. Selective capture in high-density planetary accretion zones of densities > 1E-17 kg m-3 is achieved by viscous drag. Strategies are evaluated to seed dense cloud cores, or individual protostellar condensations, accretion disks or young planets therein. Targeting the Ophiuchus cloud is described as a model system. The biological content, dispersed in 30 μm, 1E-10 kg capsules of 1E6 freeze-dried microorganisms …

Kinetics Of Cleavage Of Intra- And Extracellular Simian Virus 40 Dna With The Enediyne Anticancer Drug C- 1027, Jerry Goodisman, James C. Dabrowiak, Christopher A. Kirk, Terry A. Beerman, Loretta S. Gawron

Chemistry - All Scholarship

A kinetic analysis of cleavage of simian virus DNA (SV40 DNA) inside and outside green monkey BSC-I cells by the enediyne-protein antibiotic C-1027 and its free chromophore is described. Information on rate constants was obtained by fitting populations of forms I (closed circular DNA), II (nicked circular DNA) and III (linear DNA) of SV4f.J DNA as a function of drug concentration to a kinetic model which includes: cutting of form I to give form II with rate constant k1. cutting of form I to give form III with rate constant k4, and cutting of form II to give form III …

Complexes Between Nascent Polypeptides And Their Molecular Chaperones In The Cytosol Of Mammalian Cells, Daryl K. Eggers, W. J. Welch, W. J. Hansen

Faculty Publications, Chemistry

Folding of newly synthesized proteins in vivo is believed to be facilitated by the cooperative interaction of a defined group of proteins known as molecular chaperones. We investigated the direct interaction of chaperones with nascent polypeptides in the cytosol of mammalian cells by multiple methods. A new approach using a polyclonal antibody to puromycin allowed us to tag and capture a population of truncated nascent polypeptides with no bias as to the identity of the bound chaperones. In addition, antibodies that recognize the cytosolic chaperones hsp70, CCT (TRiC), hsp40, p48 (Hip), and hsp90 were compared on the basis of their …

Sodium Nitrite Alone Protects The Brain O _I_ Microsomal Ca -Atpase Against Potassium Cyanide-Induced Neurotoxicity In Rats, Odutayo O. Odunuge, G.. A. Adenuga

Faculty Publications

The effect of a short-term oral administration of potassium cyanide (KCN) (200 ppm in diet) with or without sodium nitrite (NaNO2) pretreatment on rat brain microsomal Ca2* ATPase was investigated. The specific activity value of the enzyme significantly decreased (p<0.05) by 50% compared with control and by 63% for KCN-treated rats compared with KCN-treated rats pretreated with NaNO;,. There was no significant difference at the h = 0.05 level between the values obtained for the control and KCN-treated rats pretreated with NaNO,. These results show both that feeding lowers brain microsomal Ca2f-ATPase activity and that NaNO, has a protective role (antidote function) in that respect.

Molecular Engineering Of Side-Chain Liquid Crystalline Polymers By Living Polymerizations, Coleen Pugh, Alan L. Kiste

Chemistry and Biochemistry

“Living” anionic, cationic, metalloporphyrin and ring-opening metathesis polymerizations have been used to prepare well-defined side-chain liquid crystalline homopolymers, block and graft copolymers and statistical copolymers. This paper analyzes their successes and failures by reviewing the mechanistic aspects and experimental conditions of each type of polymerization, and identifies other classes of mesogenic monomers that could be polymerized in a controlled manner in the future. The emerging structure/property relationships are then identified using well-defined SCLCPs in which only one structural feature is varied while all others remain constant.

The thermal transitions of liquid crystalline polymethacrylates, polynorbomenes and poly(viny1 ether)s reach their limiting …

Infrared Spectroscopy Of Nickel And Iron Geoporphyrins, Kewei Xu

Theses, Dissertations and Capstones

The first assignments of a number of vibrational modes to the infrared spectra of nickel and iron porphyrins are presented. The purpose of this work was to establish a library of reference spectra which can be used in the identification of geoporphyrins from coal. The infrared regions of 1700-1200 cm·' and 1200-600 cm·1 are informative and display a rich array of skeletal and alkyl substituent modes. The detailed analyses indicate that nickel and iron complexes of the four etioporphyrin (Etio) I-IV isomers exhibit notable differences at certain positions, especially in the 800-700 cm·' and 1000-900 cm·' subregions, which should enable …

The Resolution Of Chiral Dialkylarylsufonium Ions By 1h Nmr Spectroscopy, Johnathan Whetstine

Mahurin Honors College Capstone Experience/Thesis Projects

The goal of this research was to design a rapid Nuclear Magnetic Resonance method to measure enantiomeric excess of chiral sulfonium ions by using chiral lanthanide shift reagents. The sulfonium ions studied were dialkylarylsulfonium ions. The shift reagent that was employed was Europium (III) surrounded by chiral ligands of 3-trifluoroacetyl-d-camphor (tfc), which is derived from (+)-camphor. Ethylmcthylphenylsulfonium ion was synthesized for study as a racemic and enantiomerically enriched mixture. The sulfonium ion was then ion-paired with the shift reagent for resolution of R and S enantiomers. The best resolution was obtained with the Eu(fod)4- shift reagent, with nearly baseline resolution …

A Comparison Of The Kinetics Of Fatty-Acid Metabolism In Smokers And Nonsmokers, Patricia A. Valusek

Honors Theses, 1963-2015

For many years, the United States government has required labels on all cigarette packages warning against the many ill effects associated with smoking. One of the major factors contributing to the unhealthy aspects of smoking is its profound impact on nutrient levels within the body. Free radicals found in both the gas and tar phases of cigarette smoke may pose a significant threat to the fatty-acid levels in the body. One method of assessing this threat is to examine the fatty-acid synthesis rates of smokers and nonsmokers. An assumption was made that a destruction of fatty-acids will be displayed as …

Comparative Analysis Of Pesticide Extraction Methods, Julie A. Lapos

Honors Theses, 1963-2015

Liquid-Liquid Extraction using methylene chloride, Liquid-Liquid extraction using a 75:25 mexanes: ethyl acetate solvent, and Solid Phase Extraction using C-18 disks were compared. Aliquots of water spiked with alachlor, atrazine, and trifluralin were extracted using each of the techniques. The extracts were concentrated and analyzed using Gas Chromatography/Mass Spectrometer with Selected Ion Monitoring. A surrogate, 2-nitro-m-xlene, and an internal standard, phenanthrene-d10,, were used. At spiking levels of 5-60 ug/L, there was not a significant statistical difference between the three methods when the liquid extractors were run for 24 hours. There was however a difference between the solid phase extraction and …

Application Of Environmental Organic Petrology And Geochemistry To Fingerprint Organic Pollutants In The Recent Sediments Of Lake Ontario, Prasanta K. Mukhopadhyay, Michael A. Kruge, C.F. Michael Lewis

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

Selected surface sediment samples (sediment depth 0-10 cm) collected in the Niagara basin (western Lake Ontario) were chosen for organic matter characterization using organic petrological and geochemical techniques normally reserved for the study of coal, petroleum source rock and crude oil. The study was performed to assess the effectiveness of these techniques in discriminating between natural and anthropogenic organic matter and to determine the extent of organic pollution of the lake sediments. The organic carbon contents of the samples vary from 1.5 to 3.5%, with upper layer (0-5 cm) samples have higher TOC values than those from the lower layer …

The Computational Study Of "Model" Pollutants In Clay Montmorillonite, Sung-Ho Park

Dissertations

No abstract provided.

Separation And Artificial Maturation Of Macerals From Type Ii Kerogen, Michael A. Kruge, Patrick Landais, David F. Bensley, B Artur Stankiewicz, Marcel Elie, Olivier Ruau

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

Immature Type II kerogen (HI= 660 mg/g) from the Lower Toarcian of the Paris Basin was separated into an alginite concentrate (HI = 952 mg/g) and an amorphous organic matter (AOM) concentrate (HI = 573 mg/g) by density centrifugation. The flash pyrolyzate of the alginite is characterized by high relative concentrations of several series of n-alkanones and n-alkenones (including mid-chain alkyl ketones), in addition to n-alkanes, n-alk-1-enes and n-alkadienes. To our knowledge, this Toarcian alginite is the oldest example of marine organic matter whose pyrolyzate contains mid-chain alkanones in such high relative concentrations. In sharp …

Characterization Of Iron Oxides And Atmospheric Corrosion Of Steel, Sei Jin Oh

Physics Theses & Dissertations

The study of corrosion behavior was performed using three different analytical techniques, which provided information on the formation, development and layering of iron oxides on the corrosion products as a function of atmospheric conditions, exposure time and type of steel. In particular, the protective layer formed on weathering steel was investigated as a function of different amounts of alloying elements in the steel, atmospheric conditions and exposure times. Combined together, the results provided a better understanding of the atmospheric corrosion behavior of steel, and formed a part of database of the atmospheric corrosion characteristics.

Accurate characterization of the iron oxides …