Chemistry Commons^™

Reactions Of Modified Silica Gel Surfaces With Organometallic Compounds: Enhancing Olefin Polymerization Catalysts, Richard E. Diebel Iii

Masters Theses

Pretreated silica gels with distinct silica surfaces containing either isolated silanols, vicinal silanols, siloxanes, or some combinations of the three, were reacted with several organometallic compounds to determine how each compound reacted with the different silica surface species. The organometallic compounds used were trimethylaluminum, triethylaluminum, diethylaluminum chloride, ethylaluminum dichloride, methylaluminoxane, dibutylmagnesium, and bis-cyclopentadienyl dimethyl zirconium.

These reacted silica gels were analyzed using diffuse reflectance infrared Fourier transform spectroscopy and ICP-AES elemental analysis. CH/Metal ratios were calculated using specific peaks in the IR spectra to elucidate the surface bonded species. Elemental analysis was used to determine how much metal was bonded …

Metathesis-Based Synthesis Of Jasmonate And Homojasmonate Lactones, Candidates For Extracellular Quorum Sensing Molecules In Candida Albicans, Su C. Cho, Patrick Dussault, Amber D. Lisec, Ellen C. Jensen, Kenneth W. Nickerson

Department of Chemistry: Faculty Publications

Ring-closing metathesis of jasmonate esters is shown to provide a rapid entry to jasmonate lactones. The lactones were investigated as possible quorum sensing molecules for the fungi Candida albicans. Assays demonstrated no effect on fungal morphology at concentrations up to 96 mM.

Substituted Polythiophenes From Highly Reactive Zinc Reagents, Reuben D. Rieke

Department of Chemistry: Faculty Publications

A novel Zerovalent zinc species and an organozinc reagent are disclosed. The zerovalent zinc species is directly pro duced by reaction of a reducing agent on a zinc salt, preferably Zn(CN)₂. The organozinc reagent results from the reaction of the zerovalent zinc species and an organic compound having one or more stable anionic leaving groups. These organozinc reagents include a wide spectrum of functional groups in the organic radical, and are useful in a variety of reactions schemes.

Cross-Coupling Of Organic Compounds Using Cuprous Odide, Reuben D. Rieke

Department of Chemistry: Faculty Publications

Cross-coupling or addition reactions of organic compounds, including acid halides, allylic halides, and C.B-unsaturated carbonyl containing compounds, with organozinc com pounds may be readily and Safely carried out in the presence of cuprous iodide. The use of this catalyst in the coupling reaction provides for the preparation of commercially useful products in the pharmaceutical, agrochemical and other industries.

The Electrode Process Of Some Organic Dyes Studied By Spectroelectrochemical Technique In Situ, Yinxuan Tang, Hangsheng Yang, Baoen Shen

Journal of Electrochemistry

Spectroelectrochemistry especially with in situ measurement in a cell provides a very useful mthodology for measuring the parameters of electrode process. In this paper, we report the determination of formal potentials, the number of electron transfer, the diffusion coefficient, the heterogeneous electron transfer rate constant and the transfer coefficient of some organic dyes (Methyelene blue, Neutral red, Indigo carmine) using spectroelectro chemical technique in situ.

Nondipole Resonant X-Ray-Raman Spectroscopy: Polarized Inelastic Scattering At The K Edge Of Cl2, J. D. Mills, J. A. Sheehy, T. A. Ferrett, S. H. Southworth, R. Mayer, Dennis W. Lindle, P. W. Langhoff

Chemistry and Biochemistry Faculty Research

Experimental and theoretical studies are reported on the inelastic (Raman) scattering of wavelength-selected polarized x rays from the K edge of gas-phase chlorine molecules. The polarized emission spectra exhibit prominent nondipole features consequent of phase variations of the incident and emitted radiation over molecular dimensions, as predicted by the Kramers-Heisenberg scattering formalism. Issues pursuant to the detection of core-hole localization by resonant Raman scattering from homonuclear diatomic molecules are critically examined. [S0031-9007(97)03486-8]

Fabrication And Evaluation Of Boron-Doped Cvd Diamond Microelectrodes, Song Pang

Chemistry & Biochemistry Theses & Dissertations

The electrochemical behavior of boron-doped diamond microelectrodes has been studied in acetonitrile solutions containing two redox couples using cyclic voltammetry. One test system is 1-2.5 mM ferrocene, containing 0.1 M Tetrabutyl ammonium hexafluorophosphate (TBAH). This well-known reversible redox system involves only one electron transfer with little or no change in the solvation sphere and no breakage/formation of chemical bonds. Another test system is a 1 mM S₂Mo₁₈0₆₄^4- solution containing 0.1 M HCIO₄. This is one of the most complicated redox systems. In the presence of acid, electrons are usually transferred consecutively and …

Effects Of Tunneling Electrons And Local Field On Nanometer Region Solid / Liquid Interfacial Reactions ——Potential Controlled Stm Induced Nanoscale Modification Of H Terminated Si(111) Surfaces, Zhaoxiong Xie, Xiongwei Cai, Caihui Shi, Bingwei Mao, Zhaowu Tian

Journal of Electrochemistry

H-terminated n-Si(111) surface was found to be etched in 0.5% HF solution in nanometer scale while scanning the STM tip when the substrate potential was somehow lower than the open circuit potential at tunneling condition of V_b=+1.0 V (tip positive), I_t=1 nA. Much more stable Si surface was achievable at potentials much more negative than the open circuit potential (such as 500 mV negative to OCP) under the same tunneling condition. Furthermore, the etching rete at less negative potential was found to be somehow related to the tunneling current. These results indicate that the STM induced …

Development Of Solid Phase Microextraction Methods For Contraband Drugs, Vangielynn Cruz Tersol

Chemistry & Biochemistry Theses & Dissertations

The objective of this study is to develop analytical methods for studying contraband drugs at nanogram levels and to demonstrate the utility of the methods. A method which combines solid phase microextraction with ion mobility spectrometry (SPME-IMS) was developed. The SPME-IMS method was used as a rapid screening tool in studying the chemistry of cocaine HCI, heroin HCI, and heroin freebase on surfaces. The total time for sample preparation, reaction, and analysis is approximately seven minutes. Another method that was developed is one that combines solid phase microextraction with gas chromatography (SPME-GC) for the quantitative analysis of cocaine freebase and …

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) …

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 …

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 …

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 …

Construction Of Gold Micro-Bead Ultramicroelectrodes, Deon T. Miles, Andrew Knedlik, David O. Wipf

CAS Publications

A new way to construct small electrodes by the use of metal micro-beads is described. Gold beads of 1.5 to 3.0 mm diameter were used to construct inexpensive and disposable microelectrodes with overall structural diameters of £ 6 mm and electrode diameters of £ 5 mm. The voltammetric response of these electrodes is consistent with existing theory and the electrodes exhibited the sigmoidal waves expected at ultramicroelectrodes.

Α-Vinyllysine And Α-Vinylarginine Are Time-Dependent Inhibitors Of Their Cognate Decarboxylases, David B. Berkowitz, Wan Jin Jahng, Michelle L. Pedersen

Department of Chemistry: Faculty Publications

(±)-α-Vinyllysine and (±)-α-vinylarginine display time-dependent inhibition of L-lysine decarboxylase from B. cadaveris, and L-arginine decarboxylase from E. coli, respectively. A complete Kitz-Wilson analysis has been performed using a modification of the Palcic continuous UV assay for decarboxylase activity.

Cross Sections For The Production Of He+ (Np) 2p0 States By 50 To 150 Kev Proton Impact On Helium, Wayne C. Stolte, R. Bruch

Chemistry and Biochemistry Faculty Research

Cross sections have been measured for the production of He⁺ (np) ²P^o states, n=2,3,4, by proton impact on helium over a projectile velocity range of 1.42–2.45 a.u. (50 ≤E≤150 keV). Cross sections were determined by measuring the extreme ultraviolet photons emitted from excited He1 ions. The data indicate a lower energy than expected for the maximum cross section. A comparison of the present results in terms of projectile energy dependance with the cross sections for excitation to He (1snp) ¹P^o, ionization, and total electron capture suggests the primary mechanism …

A Review Of Differential Electrochemical Mass Spectroscopy Techniqueⅰ. The Principle And Development Of Dems, Fujikawa Keikichi, Li Feng

Journal of Electrochemistry

No abstract provided.

Time-Resolved Electron Spin Resonance Spectroscopy For In-Situ Studies Of Electrochemical Systems, Lin Zhuang, Juntao Lu

Journal of Electrochemistry

No abstract provided.

Surface Raman Spectra Obtained From Various Electrodeposited Transidon Metals, Jingsong Gao, Bin Ren, Qunjian Huang, Zhongqun Tian

Journal of Electrochemistry

Good quality potential-dependent surface Raman spectra of pyridine were obtained for the first time from a series of transition metals, e. g., Fe, Co, Ni, Ru, Rh, Pd and Pt, which were electrodeposited on non-SERS-active substrates. The influences of the applied potential and the nature of metal on the adsorption behaviors were discussed briefly. This result illustrates that Raman spectroscopy is becoming a more general and powerful tool to study various electrochemical interfaces.

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.

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 …

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).

The Applications Of Poap Ni2+ Films Modified Electrode As Sensor For Alcohol, Bingzeng Hua, Wenyun Hu, Yanzhen Chen

Journal of Electrochemistry

POAP Ni²⁺ films modified electrode can electrocatalyzes significantly the oxidation of alcohol. The modified electrode can be used as the electrochemical sensor for the detection of alcohol. But the oxidation of alcohol is effected by the thickness of films、the concentration of nickel ion in films, pH of electrolyte, as well as temperative. All of those conditions have been studied in order to achieve stable response current during the oxidation of alcohol, and the relation between concentration and current has been made. At last the major characteristic parameters, such as the low limitation of concentration, the response time, the ability …

Surface Raman Spectra Of Pyridine And 2 Mercaptopyrimidine Adsorbed On Rough Nickel Electrode, Qunjian Huang, Jinsong Gao, Xiongwei Cai, Bingwei Mao, Mingsen Zheng, Zhongqun Tian

Journal of Electrochemistry

The Raman spectra of pyridine and 2-mercaptopyrimidine (2-MP) adsorbed on bare nickel electrodes roughened by a HNO₃ etching procedure have been obtained for the first time by utilizing a highly sensitive confocal Raman microscope. Their adsorption behaviours are discussed briefly. This primary result illustrates a great potential for in-situ Raman spectroscopy in the study of chemical and electrochemical processes of transition metal surfaces.

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. …

Statistical Mechanical Treatment For The Electrical Double Layer At Ities: Analysis Of Mvn Model, Jintian Wu, Shengpei Chen, Hui Wang, Wenduan Su

Journal of Electrochemistry

A statistical mechanical treatment for electrical double layer at the interface between two immiscible elecrolyte solution (ITIES) is presented by using grand canonical method based on the MVN model.

For the MVN model, the ITIES was represented by that the two space charge regions are separated by an inner layer of the oriented solvent molecules. Assuming that the ions were allowed to penetrated into the solvent compact layer over some distance, then the grand canonical partition function of the inner layer at ITIES can be given. While the mean field approximation is employed to estimate the interactive potential energy of …

Indirect Ultraviolet Detection Of Biologically Relevant Organic Acids By Capillary Electrophoresis, Hong Chen, Yan Xu, Frederick Van Lente, Michael P.C. Ip

Chemistry Faculty Publications

Indirect UV detection of fourteen short-chain organic acids (e.g., oxalic acid, citric acid, malonic acid, tartaric acid, methylmalonic acid, α-ketoglutaric acid, succinic acid, ethylmalonic acid, methylsuccinic acid, glutaric acid, apidic acid, methylglutaric acid, lactic acid and pyruvic acid) by capillary electrophoresis is described. The method used phthalate as the UV-absorbing additive in carbonate buffer and the non-absorbing analytes were detected indirectly at 230 nm. The influences of buffer pH, ionic strenght, concentration of phthalate and organic modifier on indirect signal response and migration behavior of the organic acids were investigated. Comparisons of reproducibility on migration time, limit of detection and …

Study Of Electrochemical Behaviour Of Myoglobin Using Cyclic Voltammetry And Synchronous Fluorescence Spectroscopy, Ju Chou, Haihong Zhou, Tianhong Lu, Yue Wu

Journal of Electrochemistry

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Highly Reactive Form Of Copper And Reagents Thereof, Reuben D. Rieke

Department of Chemistry: Faculty Publications

A novel Zerovalent copper species and an organocopper reagent are disclosed. The Zerovalent copper species is directly produced by reaction of a reducing agent with a combination of copper(I) cyanide or halide and an alkali metal halide salt. The organocopper reagent resulting from the reaction of the zerovalent copper species and an organic compound having one or more stable anionic leaving groups is a stable reagent that will not significantly homocouple and under controlled conditions tolerates the presence of nitrile, epoxide, imine, enone, ketone, ester, allyl and benzyl groups within the organo radical. The reagent can be controlled so that …

Acidic Marine Biotoxins Implicated In Diarrhetic Shellfish Poisoning, Eoin P. Carmody

Theses

An okadaic acid (OA) etiology has been demonstrated for most outbreaks of diarrhetic shellfish poisoning (DSP) in Europe, An isomer of OA, dinophysistoxin-2 (DTX-2), has recently been found in Irish waters and, in 1991 and 1994, was the major toxin during prolonged infestations in cultivated mussels (Mytilus edulis) along the south-west coast of Ireland.

The OA class of DSP toxins have been analysed by HPLC using modified versions of three established fluorescent derivatisation methods. A ‘dual tag’ method for the confirmation of specific toxins has also been developed.

Survey work has been carried out over the past four years on …