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An Esr Study Of Free Radicals In Electroreduction Process Of Allyl Alcohol, Jindong Zhang, Yafei Kuang, Shukun Huang, Naixian Xie, Fengzhen Wang, Dewen Chen

Journal of Electrochemistry

Electrochemical-ESR technique with spin trap phenyl-t-butyl nitrone(PBN)was used to study the intermediates of electroreduction of allyl alcohol at platinized platinum electrode in acidic alcohol-aqua solution. Hydrogen and allyl group and(or)propyl group radicals were identified by a hyperfine spectrum of the radical adducts, and that provided a direct evidence for the presence of these radicals in the electroreduction of allyl alcohol.

Kinetics And Jamming Coverage In A Random Sequential Adsorption Of Polymer Chains, Jian-Sheng Wang, Ras B. Pandey

Faculty Publications

No abstract provided.

Degradation Product Analysis Of Bismaleimide Composite, Wendy Zhong

Masters Theses & Specialist Projects

This study evaluates the thermal and oxidative stabilities of a bismaleimide (BMI) polymer composite reinforced with an intermediate modulus graphite fiber, Cytec®5260/IM7. The composite is aged in helium, nitrogen, and air at elevated temperatures up to 600°C. Its weight change is followed thermogravimetrically for stability assessment. The effect of aging gas environment is also studied. The use of on-line gas cell fourier transform IR spectrometer (FTIR) and mass spectrometer (MS) allows for the identification of decomposition products by evolved gas analysis. This combination of thermogravimetric analysis (TGA) and evolved gas analysis by FTIR and MS yields complementary information regarding pyrolysis …

Directed Ortho-Metalation Of The Three Methyl Anisoles In Various Media, Carl Friesen

Masters Theses & Specialist Projects

Directed ortho-metalation (DoM) is a very useful alternative to electrophillic aromatic substitution (EAS) for the synthesis of substituted aromatic compounds. DoM is highly regiospecific providing metalation chiefly in the ortho-position. However, lateral (a-) metalation of an alkyl side-chain and ortho-metalation of a second ortho-position can compete. Investigation of the three methylanisoles was therefore undertaken to determine the interplay between these factors and to discover metalation conditions to achieve selectivity. This goal was uniquely achieved for p-methylanisole where conditions were discovered which allowed > 85% ortho-metalation as determined by GC analysis with virturally no competing lateral metalation. Three derivitives of this ortho-lithio …

A Study Of The Effect Of The Extraction Procedure In The Analysis Of Organic Compounds Adsorbed On Coal Ash, Shobha Purushothama

Masters Theses & Specialist Projects

The organic compounds found adsorbed on coal fly ash have been a cause for concern since the early days of the industrial revolution. A vast majority of the compounds reported as being adsorbed on the ash are polyaromatic hydrocarbons (PAHs). This study represents an attempt to evaluate the parameters involved in the extraction, detection and quantitation of these organic compounds. Though no definite conclusions could be reached as to the most efficient method of extraction, interesting results were obtained with regarding the choice of the solvent and the temperature programming on the GC/MS used for analysis. The solvent of choice …

The Role Of Written And Verbal Expression In Improving Communication Skills For Students In An Undergraduate Chemistry Program, Brian P. Coppola, Douglas S. Daniels

Chemistry Faculty Publications

Proofreading, editing, and critique, the customary assessment tools scientists use to evaluate professional journal articles, grant applications, and any other writing, can be applied equally well in introductory science instruction. Such feedback is, in fact, crucial to growth and development. When learning anything new, students and faculty alike rely heavily on sources other than themselves (‘external editors’) to assess their understanding as they develop self-assessment skills (or ‘internal editors’). Although they rarely describe it in these terms, faculty nonetheless assume that students have developed and refined their internal skills by the time they take examinations and write term papers. Unfortunately, …

Reactions Of Chlorine And Some Of Its Oxygen Derivatives With Phenol, Lizhuo Zhang

Masters Theses

Chlorine is widely used in industry. It is also the most commonly used disinfectant in water treatment plants. Since the amount of chlorine used is increasing each year, environmental and health concerns arise due to its reactivity with various of organic compounds. Many chlorinated organic compounds are toxic and as a result other non-chlorinating compounds, such as chlorine dioxide, might be potential substitutes in the future, especially in water treatment plants.

Previous studies have indicated that chlorinated organic compounds are not formed when chlorine dioxide is used as a disinfectant. Furthermore no reaction occurs between chlorite and phenol in the …

Synthesis And Characterisation Of New Dimolybdenum (Ii,Ii) Dicarboxylates And Their Use As Polymerization Catalysts, Elizabeth Whelan

Masters

The purpose of this work was to prepare a series of new dimolybdenum(II,II) dicarboxylate complexes, to characterize the complexes and to investigate their use as potential catalysts for the ring-opening metathesis polymerization (ROMP) of the bicyclic monomer norbornene.

Neutron Diffraction Structural Study Of Ce₂Fe₁₇₋ₓgaₓ, H. Luo, Z. Hu, William B. Yelon, Sanjay R. Mishra, Gary J. Long, Oran Allan Pringle, D. P. Middleton, K. H. J. Buschow

Physics Faculty Research & Creative Works

Six samples of Ce₂Fe_17-xGa_x with nominal Ga content x equal to 0, 0.3, 0.5, 0.7, 1.0, 2.0 have been studied by powder neutron diffraction at room temperature. Both crystalline and magnetic refinements have been carried out. All six samples adopt the Th₂Zn₁₇-type rhombohedral structure. The only additional phase found is α-iron. Gallium atoms are found to have high affinity for the iron 18h site, and are absent from the 9d and 18f sites. The Ga substitution for Fe leads to an expansion of both the a and c axes. The Curie …

Comparison And Modeling Study Of Vancomycin, Ristocetin A, And Teicoplanin For Ce Enantioseparations, Mary P. Gasper, Alain Berthod, Usha B. Nair, Daniel W. Armstrong

Chemistry Faculty Research & Creative Works

The structurally related glycopeptide antibiotics vancomycin, ristocetin A, and teicoplanin can all be used as chiral selectors in capillary electrophoresis (CE). Both experimental and modeling studies were done to elucidate their similarities and differences. There are identifiable morphological differences in the aglycon macrocyclic portions of these three compounds. In addition, there are other structural distinctions that can affect their CE enantioselectivity, migration times, and efficiency. Teicoplanin is the most distinct of the three and is the only one that is surface active. Its aggregational properties appear to affect its enantioselectivity among other things. The similar but not identical structures of …

A Hplc Method To Assay Mycotoxins - Fumonisin, Ochratoxin And Zearalenone, Nalini Sadagopan

Masters Theses

A HPLC method to quantitate the mycotoxins Fumonisin B1 (FB1), Ochratoxin A(OA), and Zearalenone (ZON) was developed and validated. Mycotoxins are secondary metabolites of fungi like Fusarium, Asperigillus and Penicillium that contaminate crops. They have a wide array of chemical structures which facilitate their analytical detection.

The analytical method consists of reverse phase chromatography and fluorescence detection. Sample cleanup was performed using SAX and C18 cartridges prior to analysis on the HPLC.

The method developed for FB1 is unique in that it is more sensitive, accurate, and reproducible than the existing methods. Automation is one of the salient features that …

38th Rocky Mountain Conference On Analytical Chemistry

Rocky Mountain Conference on Magnetic Resonance

Final program, abstracts, and information about the 38th annual meeting of the Rocky Mountain Conference on Analytical Chemistry, co-sponsored by the Colorado Section of the American Chemical Society and the Rocky Mountain Section of the Society for Applied Spectroscopy. Held in Denver, Colorado, July 21-26, 1996.

Model Calculations Of Langmuir Monolayers: Pressure Effects On Tilting Behavior Of Idealized Amphiphiles, D.R. Swanson, Robert J. Hardy, Craig J. Eckhardt

Craig J. Eckhardt Publications

Model amphiphiles consisting of lines of Lennard-Jones (LJ) centers are investigated to determine the effect of pressure and molecular geometry on ground-state tilting behavior. Both the amphiphile length and the intramolecular distance between LJ centers is varied. The results give guidelines for understanding and controlling tilting behavior in monolayer films.

Contrast-Enhanced Magnetic Resonance Imaging Confirmation Of An Anterior Protein Pathway In Normal Rabbit Eyes, Nancy H. Kolodny, Thomas F. Freddo, Barbara A. Lawrence, Cristina Suarez, Stephen P. Bartels

Chemistry: Faculty Publications

Purpose: Contrast-enhanced proton magnetic resonance imaging ( 1H MRI) has been used as a quantitative, noninvasive method to corroborate a pathway for the diffusion of plasma-derived protein into the aqueous humor in the normal rabbit eye. Methods. T1-weighted magnetic resonance images were produced over 1- to 3-hour periods after the intravenous injection of gadolinium diethylenetriamine-pentaacetic acid. Results. Analysis of the images yielded the time dependence of signal enhancements within the areas of interest. The ciliary body showed an immediate sharp increase, followed by a gradual decrease in signal enhancement with time. Although a gradual increase in signal enhancement was found …

Automation And Analysis Of Thermometric Titrations, Russel P. Linneman Ii

Honors Theses

Over the past three years, I have been involved in the development and testing of an automated thermometric titration system for chemical research. There were three major phases in this process. The first phase consisted of modernizing the equipment and software. The second phase consisted of testing the software and equipment with a known chemical system. The third phase consisted of original research.

Structure, Dynamics, And Phase Transitions In The Fullerene Derivatives C_{60}O And C_{61}H_{2}, C. Meingast, G. Roth, L. Pintschovius, R. H. Michel, C. Stoermer, M. M. Kappes, Paul A. Heiney, Laurent Brard, Robert M. Strongin, Amos B. Smith Iii

Chemistry Faculty Publications and Presentations

The effect of perturbing the icosohedral symmetry of C₆₀ by the addition of the side groups -O and -CH₂ upon orientational order-disorder and glass transitions in solid C₆₀ has been studied by a combination of high-resolution capacitance dilatometry and single-crystal x-ray and powder inelastic neutron scattering. Both fullerene derivatives C₆₀O (epoxide) and C₆₁H₂ (6,5-annulene) are shown to undergo a sequence of transitions similar to that found in pure C₆₀, i.e., a first-order orientational ordering transition just below room temperature followed by an orientational glass transition at lower temperatures. Although the …

Comparison Of Positive Screening And Confimatory Results From Federally Mandated Drug Testing Of Urine, Mary M. Stuck

Community & Environmental Health Theses & Dissertations

The purpose of this study was to analyze the accuracy of FDA approved immunoassays for the detection of drug positive urine samples.

Federal civilian employees are tested under the strict protocol of the Department of Health and Human Services mandatory guidelines for federal workplace drug testing programs. The guidelines provide for a two instrument testing protocol for the analysis of urine samples. The first is an FDA approved immunoassay. Samples which test positive on this screening immunoassay are then submitted for confirmatory testing with the "gold standard" gas chromatography/mass spectrometry.

Agency monthly drug testing summaries, required under the DHHS guidelines …

Concentrations, Complexation And Speciation Of Total Dissolved Zinc In The Chesapeake Bay, Charles William Henry Iii

Chemistry & Biochemistry Theses & Dissertations

This is the first research to examine the horizontal, vertical, and temporal variability of total dissolved zinc, organic complexation of zinc, and zinc speciation in the Chesapeake Bay. Filtered (0.45μm) surface and bottom water samples were taken along the salinity gradient of the Chesapeake Bay in October 1993, March 1995, July 1995, and October 1995. Analysis by Differential Pulse Anodic Stripping Voltammetry (DP ASV) indicated that total dissolved zinc concentrations in the Bay ranged from 2.9 ± 0.7nM to 38.8 ± 2nM. Total zinc was highest at the northern end of the Bay (low salinity), approximately 10 times lower at …

Reactions Of Aqueous Chlorine With Alanylphenylalanine In Model Solutions And In A Wastewater, Thomas C. Fox

Chemistry & Biochemistry Theses & Dissertations

Model solutions of the dipeptide alanylphenylalanine were chlorinated to four different chlorine-to-amino nitrogen (Cl₂/Ala-Phe) mole ratios and analyzed by high performance liquid chromatography. At mole ratios ≤ 1, N-chloroalanylphenylalanine was the only major product. As the Cl₂/Ala-Phe mole ratio was increased to ≥ 2, N,N-dichloroalanylphenylalanine was the only major product. In model solutions (pH 7.0) the dichlorinated dipeptide decomposed (t_1/2= 4.1 hr) to form a stable N-chloroketimine, which has a half-life of 125 hours. This N-chloroketimine then decomposed to form phenylalanine.

To follow these reactions in a wastewater, alanyl-p-[ …

Two-Dimensional 1H Nmr Studies On Octahedral Nickel(Ii) Complexes, Richard C. Holz, Evgenij A. Evdokimov, Feben T. Gobena

Chemistry Faculty Research and Publications

The dinucleating ligand ethylene glycol−bis(β-aminoethyl ether) N,N,N‘,N‘-tetrakis[(2-(1-ethylbenzimidazoyl)] (EGTB-Et; 1) was used to synthesize the dinuclear Ni(II) tetraacetonitrile complex cation [Ni₂(EGTB-Et)(CH₃CN)₄]²⁺ (2):  triclinic space group P1̄ (a = 12.273(5) Å, b = 12.358(7) Å, c = 12.561(6) Å, α = 90.43(4)°, β = 110.26(3)°, γ = 99.21 (4)°, and Z = 1). The structure shows two identical octahedral Ni(II) centers each bound to two benzimidazole ring nitrogen atoms, one amine nitrogen atom, an ether oxygen atom, and two acetonitrile nitrogen atoms. The …

Synthesis Of Higher Α-Chlorovinyl And Α-Bromovinyl Amino Acids: The Amino Protecting Group Determines The Reaction Course, David B. Berkowitz, Michelle L. Pedersen, Wan Jin Jahng

Department of Chemistry: Faculty Publications

N-Trifluoroacetyl α-vinyl amino esters are smoothly converted to the corresponding α-chlorovinyl or α-bromovinyl amino esters through the agency of phenyselenyl chloride or phenylselenyl bromide, respectively, followed by oxidation and pyrolysis. Exclusively the (E)-extemal halovinyl isomer and the internal halovinyl isomer are observed. The amino protecting group is a critical determinant of the reaction course (alkene addition vs. 5-exo-trig-like cyclization).

Cleavage Of Dna By The Insulin-Mimetic Compound, Nh4[Vo(O2)2(Phen)], Catharina Hiort, Jerry Goodisman, James C. Dabrowiak

Chemistry - All Scholarship

The kinetics and mechanism of cleavage of DNA by the insulin-mimetic peroxo-vanadate NH4[VO(O2)2(phen)], pV, are described. In the presence of low energy UV radiation or biologically common reducing agents, pV decomposes into the monomer, dimer, and tetramer of vanadate and an uncharacterized compound of V4+ as shown by 51V NMR, ESR, and absorption spectra. The rate of photodecomposition of pV is reduced in the presence of calf thymus DNA, indicating that a decomposition product of the peroxo-vanadate, that is important in the destruction pathway of the complex, is interacting with DNA. This species, probably a short-lived complex of V4+, may …

Experimental Evidence For Self-Similar Structures In The Aggregation Of Porphyrins In Aqueous Solutions, F. Mallamace, N. Micali, S. Trusso, L. M. Scolaro, A. Romeo, A. Terracina, Robert F. Pasternack

Chemistry & Biochemistry Faculty Works

We have studied the aggregation of the porphyrin t-H₂Pagg in aqueous solution by light scattering. The intensity profile of the elastically scattered light, studied in the exchanged wave-vector range 0.2 ≤ q ≤ 31.4 μ m⁻¹, indicates that the aggregation produces large monodisperse clusters having a fractal structure, and is driven by diffusion-limited aggregation kinetics. Additional measurements performed at different q values confirm such a picture giving a hydrodynamic radius R(H) consistent with the radius of gyration R(g) measured by elastic scattering. This is explained taking into account the q² dependence observed in the mean decay rate of the intensity-intensity …

A Graph Theoretic Study Of The Similarity Of Discrete Structures, Heather D. Gavlas

Dissertations

A basic problem in drug design consists of finding a compound that satisfies a spectrum of biological and chemical properties. Although drug design problems are central to pharmaceutical research, statisticians have yet to become involved in this area as these problems are viewed statistically as optimization problems. Before statistical optimization procedures can be defined on these spaces whose points are structures and not vectors, very basic mathematical notions of distance must be defined. Graphs have been used as mathematical models to represent the bonding arrangements of molecules for quite some time. In fact, if some of the methodology used by …

An Investigation On Nonenzymatic Autoxidation Of Phenolic Compounds In Natural Waters, Lei Jiang

Masters Theses

The nonenzymatic autoxidation of the phenolic compounds chlorogenic acid in aqueous solution was studied. The study demonstrated that the oxidation rate of chlorogenic acid was strongly dependent on pH. The higher the pH, the faster the rate of oxidation. The involvement of phenolate ions and radicals in oxidation reactions are two possible reasons for the pH dependency. The presence of a trace amounts of reducible transition metal ions, such as copper(II), dramatically increases the oxidation rate of chlorogenic acid. Light also increases the oxidation rate of chlorogenic acid. However, the photochemical reaction was a much slower process.

The TLC and …

The Reactions Of Nox With Diesel Soot Over Cu-Zsm-5 Catalyst, Shu Sun

Theses

Air pollution from the exhaust of Diesel engines consisting of relatively high concentrations of NO_x and particulates is a difficult problem to overcome because no fully effective technology to control these emission is available. The existing methods to reduce NO_x and soot can not satisfy the provisions of the 1990 CAAA (Clean Air Act Amendment). Cu-ZSM-5, a catalyst in which Cu has been ion-exchanged with H+, can catalyze the decomposition of NO to N₂ and O₂ and reduction to N₂ and O₂ with light hydrocarbons such as propene or Diesel soot in the presence …

Speciation And Determination Of Trace Lead : Methodology Development And Analysis Of Natural Waters Using Chelex-100 And Gfaas, Xidan Ma

Theses

The development of a method for speciation, preconcentration, and determination of lead was successfully conducted using Chelex-100 and graphite furnace atomic absorption spectroscopy (GFAAS). Sorption under static conditions and direct measurements in the bead slurry or after fast elution of lead from beads with HNO3 solution was used. The effects of buffers, sorption kinetics, filtration criteria, sample concentration, resin particle size and temperature program for the GFAAS were carefully studied. In this study, synthetic aqueous samples containing lead were preconcentrated under static conditions using the ion exchange resin, Chelex-100, and the resin was directly analyzed using GFAAS. The batch preconcentration …

Status Of The Research And Development For Fuel Cell Technology Abroad, Naichao Li, Baolian Yi

Journal of Electrochemistry

Status of the research and development for fuel cell technology abroad was overviewed, and at the aim of accelerating the research and development for fuel cell technology in China, the corresponding stategy for our country was recommended.

Electroluminescent Property Of N Type Porous Si And Its Characterization By Xps And Lima, Guozheng Li, Chenqian Zhang, Qiang Zhang

Journal of Electrochemistry

The chemical composition and structure of electroluminescent porous Si(PS) on n-Si, prepared by photoelectrochemical etching method, were investigated by using XPS and LIMA. The results show that electroluminescence(EL) intensity depends on the formation potential of PS. The relation between EL property and the results of XPS and LIMA is also discussed.

In Situ Studies Of Copper Electrodepostion On Hopg By Using Ecstm, Zhaoxiong Xie, Bingwei Mao, Xiangdong Zhuo, Jiqian Mu, Zhaowu Tian

Journal of Electrochemistry

In this paper, copper electrodepostion on HOPG had been in situ studied by using a homebuilt electrochemical scanning tunneling microscopy (ECSTM). Three dimensional nucleation and subsequent growth of copper crystals were found as the initial stage of copper deposition on HOPG. In the case of lower overpotential or lower concentration of Cu²⁺ , the bulk deposited copper layer tended to form smooth terraces, and grow at the edge of steps. The terraces were stable to some extent, which made it possible to be observed with atomic resolution. At a higher overpotential, the crystal size of copper were somehow smaller. …