Physical Sciences and Mathematics Commons^™

Identification And Quantitation Of Volatile Amines In Marine Sediments, Chuen Mei Huang

Chemistry & Biochemistry Theses & Dissertations

Pore waters which were taken from sediments of the Chesapeake Bay were analyzed to determine the presence of volatile amines. A purge-and-trap technique was used to concentrate the amines. Then, following derivatization with heptaflourobutyric anhydride, the HFBA-amines were analyzed by gas chromatography with electron capture detection and with mass spectrometric detection. One secondary amine, diethylamine with a concentration of 0.3-0.6 uM, was found in a total of three pore water samples from cores collected on two different dates. A primary amine, sec-butylamine with a concentration of O. 05 AIM, was also found in one of these same samples. Another primary …

Study Of Acetone Extractable Organic Matter From Airborne Particulate Matter From An Urban Site, Wenhui Wu

Theses

Two seasonal periods (Winter 1988; Summer 1988) of daily Newark urban air samples were collected on glass fiber filters. Each filter was first extracted with dichloromethane and subsequently with acetone. Quarterly composites of each were then tested for mutagenicity. The results of the analysis of the less polar dichloromethane extracts were reported in the thesis of Junghen Lwo. A modified fractionation scheme involving acid-base partitioning and silica gel column chromatography has been used as the first step in the bioassay-directed search for significant levels of mutagenic compounds in extracts of inhalable (IP 10) ambient air particulates. The biologically "hot" fractions …

Simultaneous Determination Of 3-Methoxy-4-Hydroxyphenyl-Glycol, Homovanillic Acid, And 5-Hydroxyindoleacetic Acid In Plasma By High Performance Liquid Chromatography, Yung-Te Tseng

Chemistry & Biochemistry Theses & Dissertations

A rapid, reliable, and sensitive method for simultaneous determination of 3-methoxy-4-hydroxyphenylglycol (MHPG), Homovanillic acid (HVA), and 5-hydroxyindoleacetic acid (5- HIAA) in plasma is described. The method is based on high performance liquid chromatography with electrochemical detection. Samples were filtered with Amicon Centrifree micropartition systems and extracted with organic solvent before chromatography. Chromatographic separation of sample components was achieved isocratically in a C18 reverse-phase column. Quantitation was performed by measuring the peak height ratios of the sample components to an internal standard. Analytical recoveries ranged from 50.78 (SD 4.2%) to 67.94 (SD 3.28). Within-run coefficient of variations (CVs) ranged from 3.78 …

Mounting Sex Pheromone: A Novel Pheromone Responsible For Mate Recognition In The Ixodidae, Jgc Hamilton

Theses and Dissertations in Biomedical Sciences

Cholesterol oleate was demonstrated to be the cuticular contact sex pheromone of Dermacentor variabilis. This pheromone which has been termed the Mounting Sex Pheromone (MSP) was also demonstrated to be present on the surface of D. andersoni, Amblyomma maculatum and A. americanum. This contact sex pheromone enables males excited and attracted by 2,6-dichlorophenol to identify the female as a potential mating partner. The MSP is the second in the series of three sex pheromones guiding the hierarchy of behavioral responses which constitute tick courtship behavior. Tests with D. variabilis and D. andersoni showed that this pheromone …

Determination Of The Kinetic And Thermodynamic Properties Of Bisulfite Addition To 4-Nitrocinnamaldehyde And 4-Dimethylaminocinnamaldehyde, Lisa Renee Nicosia

Honors Theses

The objective of this study is to compare the kinetic and thermodynamic properties of bisulfite additions to trans-cinnamaldehyde and two trans-cinnamaldehyde derivatives in order to examine substituent effects on these properties. The equilibrium constants at pH 4.63 and at 25C of two para substituted derivatives were determined using a spectrophotometric technique. The equilibrium constants were determined to be 299M-1 and 1340M-1 for 4-dimethylaminocinnamaldehyde and 4-nitrocinnamaldehyde respectively. Equilibrium constants were also determined at various temperatures, and changes in enthalpy and entropy were calculated to be: -39KJ/mol and -84J/molK for 4-dimethylaminocinnamaldehyde and -18KJ/mol and KJ/molK for 4-nitrocinnamaldehyde. The forward rate constants were …

The Effects Of Hydrogen Bonding On The Spectral Properties Of 2'-Acetonaphthone, Kristine A. Loparo

Honors Theses

The effects of hydrogen bonding on the luminescent properties of 2'-acetonaphthone (2-AN) have been studied. Solvents of varying hydrogen bond donor abilities such as perfluorohexane(PFH), cyclohexane, ethanol, methanol, water, trifluoroethanol(TFE), and hexafluoroisopropanol(HFIP) have been used. An attempt is made to find a relationship between solvent hydrogen bond donor ability, the energy and efficiency of fluorescence emission and changes in 2-AN electronic absorption in these solvents. The 2-AN spectral properties have also been studied in mixed solvent systems where the molecule is dissolved in a nonpolar solvent, either PFH of cyclohexane, and one of the fluorinated alcohols (TFE or HFIP) is …

The Construction And Testing Of A System For Flash Photochemical Studies Of Organotransition Metal Compounds, Robin Lynn Miller

Honors Theses

The main objective of my research efforts was to construct a flash photolysis system which would enable one to carry out time-resolved studies of photoinitiated reactions of organometallic hydrides. Such a development involved two major tasks. First, it required establishing a functioning vacuum line. Organometallic complexes are extremely sensitive to oxygen and water. Therefore these contaminants must be removed if one is to have any success in studying their reactions. A vacuum line is the most efficient means for degassing both solvent and solute Second, it involved modifying our flash photolysis apparatus. Changes in the flash rig included upgrading the …

C13- And H-Nmr Studies Of The Bisulfite Addition Products Of Simple Carbonyl Compounds, Diane A. Piasecki

Honors Theses

No abstract provided.

Conformational Energy Calculations Of Tyrocidine, Leslie Beth Shapiro

Honors Theses

The minimum energy conformation of the cyclic decapeptide tyrocidine was calculated using the Empirical Conformational Energy Program for Peptides (ECEPP). Half of the amino acid sequence of tyrocidine is identical to the amino acid sequence found in the cyclic decapeptide gramicidin-S. Hence this study focuses on the conformation of the decapeptide that is not contained in gramicidin-S. This study calculates the conformation of a tripeptide ASN-GLN-TYR without the consideration of the presence of a beta bend formation because there is a low probability that a beta bend exists in this location. Two of the lowest energy conformations found in this …

A Mechanistic Study Of The Saponification Of Pivaloate Esters, Beni Brian Wolf

Honors Theses

The reactions of the esters of trimethyl acetic acid (pivalic acid) have been followed kinetically (Walrath 1977 and Watkins 1986) in the presence of alkali in a 3:1 ethyl cellosolve: water solvent at 64°C. Through the use of both optically active pivaloates and O18 as a tracer, the positions of bond fission during saponification for several pivolates have been determined. With the secondary butyl ester bimolecular attack on both the acyl- and the alkyl- carbon atom is observed in the presence of alkali. Partial racemization of the product secondary butyl alcohols suggests that for a saponification of secondary butyl pivaloates …

Paleogeography And Paleoenvironments Of The Lower Unit, Fossil Butte Member, Eocene Green River Formation, Southwestern Wyoming, Roberto Enrique Biaggi

Loma Linda University Electronic Theses, Dissertations & Projects

During Eocene time sediment accumulated in Fossil Lake, in what developed to be a small linear and structurally controlled basin. Fossil Lake was one of several lakes into which the Green River Formation was deposited in Wyoming, Utah and Colorado.

Detailed stratigraphic analysis of the Lower Unit of the Fossil Butte Member revealed a well developed lacustrine sequence south of Fossil Butte, and indicates four major depositional facies: (1) open lacustrine, (2) marginal lacustrine, (3) carbonate mudflat, and (4) marginal fluvio-deltaic. The open lacustrine facies is characterized by kerogen rich to kerogen poor finely laminated micrites , that consist mainly …

The Synthesis And Characterization Of Two All-Aliphatic Sterically Hindered Diesters Of Alpha, Alpha, Alpha', Alpha'-Tetramethyladipic Acid, Ronald L. Willson

Honors Theses

The bis-t-butyl- and bis-neopentyl glycol- diesters of α, α, α', α'-tetramethyladipic acid were synthesized via their diacid chlorides. α, α, α', α'-Tetramethyladipic acid was first prepared by a free radical coupling reaction of pivalic acid because it is not commercially available. The products of all syntheses were characterized by NMR and infrared spectra.

Determination Of Benzo(A)Pyrene Metabolites In The Bile Of Winter Flounder From The New York Bight, Xingmin Liu

Theses

A method for detecting the concentration of BaP Metabolites in fish tissues has been developed. The analytical procedure includes extraction of PAH and BaP Metabolites from fish bile, liver extract and muscle extract; reduction of metabolites to BaP using hydriodic acid; and subsequent analysis of the BaP by thin layer chromatography with fluorescence detection. The method is applied to tissues from fish collected from polluted as well as clean reference waters and experimental tanks with dilutions of treated industrial wastewater. Experimental results on one kind of bottom-dwelling fish, winter flounder, which comes from the Hudson-Raritan Estuary, NY, where the water …

Substituent Effects On Strained Rings. Part A ; The Kinetics Of Hydrolysis Of A Quinuclidone Using Ftir. Part B, Yeu-Yi Chiu

Theses

PART A: The energies of a series of monosubstitued propane, cyclopropane and cyclopropene compounds were calculated using ab initio molecular orbital calculations optimized at the 3-21G level using Gaussian 82 and Gaussian 86 programs. The effects of substituents on stabilization energies and geometries are rationalized with respect to the parent molecules. The result is presented which indicated that for substituted cyclopropyl and cyclopropenyl compounds, most of the substituents induce stabilization except the —NC substituent group is destabilizing in cyclopropyl and cyclopropenyl systems. Indications of relative electrostatic and resonance effects are also analyzed. A linear free energy relationship has been exam-ined …

Synthesis Of Highly-Strained Gem-Difluoro Compounds By Reaction Of Difluoromethylene With Cycloalkenes, Deyi Yang

Theses

Trans-Cyclooctene is thought to be more reactive than cis-cyclooctene due to its trans-structure. When cis or trans-clooctene reacts with difluormethylene (:CF₂), trans-9,9-difluorobicyclo[ 6,1,0] nonane was generated in much higher yield than cis-9,9-difluorobicyclo[6,1,0]nonane. [PhCF₃P⁺CF₂Br]Br^- was chosen to be the difluoromethylene precursor in this study. The reason was that the reaction condition for trans-cyclooctene and :CF₂ should be at low temperature. Only [PhCF₃P⁺CF₂Br]Br^- could generate CF₂ at lower temperature (e.g. room temperature). We succeeded in the synthesis of trans-9,9-difluorobicyclo[6,1,0]nonane and its cis isomer and …

Synthesis Of Site Specific 1, N^2-Ethenodeoxyguanosine In A Small Oligonucleotide, Kathryn A. Carolin

Wayne State University Theses

Malondiadehyde (MDA) is a known carcinogen and mutagen produced by lipid peroxidation and prostaglandin synthesis in vivo. MDA is unique from structurally related compounds, methyl glyoxal and acrolein, because it produces frameshift mutations whereas the latter compounds induce base-pair substitutions. MDA forms several adducts with deoxyguanosine but it is not certain which one causes the frameshift mutations. Ideally, a single adduct on a replicating genome could simulate the in vivo process by which MDA mutagenesis would occur. This technique is known as site-specific mutagenesis. The approach of choice for site-specific mutagenesis experiment is the gapped heteroduplex method which requires the …

A Study Of Denitrosation Of N-Nitroso Compounds By Irradiation With Long-Wavelength Uv Light, Zhenyu J. Wang

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

N-Nitrosamines and N-nitrosamides have been reported to be mutagenic. N-Nitrosamides are direct mutagens that need no activation to be mutagenic, whereas N-nitrosamines need to be enzymatically activated to exert their mutagenicity. Oxidative demethylation of nitrosamines is a commonly accepted activation mechanism. Another pathway of nitroso compounds, denitrosation, has recently been proposed. The mechanism of denitrosation, however, is still unknown.

The purpose of this study was to use a photo -reaction model to explore the possible denitrosation mechanism of N-nitroso compounds. An N-nitrosamine, N-nitrosomorpholi ne (NMOR), and an N-nitrosamide, N-methyl-N'-nitrosoguanidine (MMNG), were irradiated with long-wavelength UV light in the presence of …

Rotoreflected Double-Beam Thermal Lens Spectrometry And Simultaneous Thermal Lens And Fluorescence Detection For High Performance Microbore Liquid Chromatography, Steven Craig Hall

Dissertations

No abstract provided.

Multinuclear Magnetic Resonance Studies Of Lithium Binding And Transport In Human Erythrocytes, Maryceline Tiausas Espanol

Dissertations

No abstract provided.

Binding And Transport Properties Of Lithium In Red Cells From Hypertensive Patients And Normotensive Controls, Ravichandran Ramasamy

Dissertations

No abstract provided.

Synthesis And Study Of N-(4-Nitrobenzofurazan)-Monoaza-18-Crown-6: A Metal Sensitive Fluorophore, Shelley A. Krause

Dissertations

No abstract provided.

Structural And Functional Studies Of The Plant Lectin Peanut Agglutinin, Eugene J. Zaluzec

Dissertations

No abstract provided.

Dielectric And Kinetic Analysis Of Thermosetting Polyester Resin, Patricia Haverty Tully

Dissertations, Theses, and Masters Projects

No abstract provided.

An Analysis Of The Inhibitory Effects Of Linolenic Acid Upon Photosystem Ii Of Higher Plants, Mark Edward Iven

Dissertations and Theses

This study utilizes steady state fluorescence measurements, flash-induced P680+ absorption transients, and DCIP reduction kinetics to study the inhibitory effects of linolenic acid (LA) upon Photosystem II (PSII) in whole spinach chloroplasts and insideout wheat thylakoids. It confirms the presence within PSII of LA-induced inhibition of energy trapping and/or primary charge separation (i.e., primary inhibition), in addition to donor side inhibition. The latter is diminished in the presence of 1,5-Diphenylcarbohydrazide (DPC) and probably takes place at the oxygen evolving complex. Primary inhibition, which is more controversial, probably occurs between Ph and QA, with a likely contribution at the level of …

The Chemistry Of Sulfonyl Fluorides: Sf5 And/Or So2f Containing Compounds As Precursors To Sulfonic Acids, Robin Joyce Terjeson

Dissertations and Theses

Sulfonyl fluoride systems and their derivatives, RS0₂F, where R represents hydrocarbon/fluorocarbon moieties continue to be of considerable interest. The incorporation of the sulfonyl fluoride group (S0₂F) into molecular systems can lead to compounds that are useful as ion-exchange resins, surface active agents, fuel cell electrolytes, and strong sulfonic acids/salts.

Interest in preparing SF₅ containing sulfonyl fluorides led to the synthesis of the ᵝ-sultone, SF₅CHCF₂0S0₂, and its rearranged product. Hydrolysis of the sultone gave SF₅CH₂S0₂F which led to the sulfonic acid and salt, SF …

Fluorinated [Beta]-Sultones As Precursors To Fluorinated Sulfonic Acids, And New Fluorosulfonyl Containing Monomers/Polymers, Javid Mohtasham

Dissertations and Theses

Sulfur trioxide (SO₃) adds to fluoroolefins of the form RCF=CF₂, (where R = F, SF₅, CF₃, CF₃OCF₂, CF₂=CF(CF₂)₂, CF₃(CF₂)₃O, CF₃O(CF₂)₂OCF₂, or CH₂ClCHClCH₂), yielding the fluorinated [beta]-sultones, RCFCF₂OSO₂. In the case of CF₃(CF₂)₃OCF=CF₂, a reverse addition occurs, giving the sultone, CF₃(CF₂)₃CF₂2OCFCF₂SO₂O. The fluoro [beta]-sultones are capable of undergoing different reactions, such as rearrangement, hydrolysis, esterification, and polymerization. These reactions, will result in the formation of compounds containing the fluorosulfonyl grouping (SO₂F); it is this group that yields the corresponding sulfonic acid upon base/acid treatment.

The addition of sodium bisulfite to CF₃CF= CF₂ and CF₃(CF₂)₄CF=CF₂ in the presence of (C₆H₅CO)₂O₂ and Na₂B₄O₇·10H₂O …

Chemical Modification Of Skeletal Muscle Sarcoplasmic Reticulum Vesicles: A Study Of Calcium Permeability, Janice F. Stuart

Dissertations and Theses

Skeletal muscle contains an internal membrane system called the sarcoplasmic reticulum (SR) whose function is to regulate the Ca²⁺ concentration of the myoplasm. Ca²⁺ is transported into the SR from the myoplasm via a Ca²⁺ dependent ATPase thus lowering the myoplasmic Ca²⁺ concentration. Ca²⁺ exits from the SR via a Ca²⁺ releqse pathway resultingin the increase of myoplasmic Ca²⁺. Muscles contract when the myoplasmic Ca²⁺ concentration is > 5 uM and relax when the Ca²⁺ concentration is lowered below 1 uM. The Ca²⁺ dependent ATPase has been extensively studied but …

Monitoring Environmental Effects On High Performance Tetraglycidyl Methylenedianiline Epoxy And Pmr-15 Polyimide, William Robinson Hayes Clark

Dissertations, Theses, and Masters Projects

No abstract provided.

Fluorinated Esters: Synthesis And Identification, Jilla Schaff

Dissertations and Theses

Reactions of different alcohols with 2-hydroxy - 1- trifluoromethyl -1,2,2-trifluoroethanesulfonic acid sultone F₃CCFCF₂OSO₂ were studied. Six new esters were prepared: C₆F₅OC(O)CF(CF₃)SO₂F, CH₃CH₂OC(O)CF(CF₃)SO₂F, CF₃CH₂OC(O)CF(CF₃)SO₂F, (CF₃)₂CHOC(O)CF(CF₃)SO₂F, CH2=CHCH₂OC(O)CF(CF₃)SO₂F, (CH₂OC(O)CF(CF₃)SO₂F)₂. Analytical data, infrared, nmr and mass spectra are presented supporting the proposed structures for these new compounds.

Study Of Photolytic Interference On Ho Measurements By Lif-Fage, Carmen Ivette Martinez

Dissertations and Theses

For many years there has been a great interest among the scientific community in the study of the hydroxyl radical, HO. This interest stems from the fundamental role played by this molecule in the photochemistry of the atmosphere, mainly as a cleansing agent of environmental pollutants. Knowing the concentration of the radical would enable scientists to corroborate current atmospheric models and to predict future trends in the atmosphere. Even though there is a great interest in the determination of atmospheric concentrations of this molecule, the task has been very difficult. This is mainly due to the lack of a method …