The aim of the investigation described in this work is to gain a better understanding of the processes involved in the oxidation of organic compounds by photolytic ozonation in a laboratory scale reactor. The results and discussions are presented in Chapter III. This chapter contains four parts. In the first part, mass transfer efficiency and the calculation of the mass transfer coefficient, KLa, as well as the ozone decomposition rate constant, KD, are presented and compared with those obtained by other investigators. The second part deals with the kinetics of the photolysis of 2,2',4,4',6,6'-hexachlorobiphenyl both in purified and natural lake water. Mathematical expressions and a discussion of the possible reaction processes involved are given. Kinetic models of ozonation and photolytic ozonation in purified and natural lake water are developed and discussed in part three. Rate constants are calculated from experimental data and used to predict values of substrate destruction with a mathematical model. The fourth part of this chapter deals with the identification of products from the photolysis, ozonation and photolytic ozonation of 2,2'4,4',6,6'-hexachlorobiphenyl. The products are isolated and identified using combined gas chromatography and mass spectroscopy, and reaction mechanisms are suggested.

Cyclopropanation of the unsaturated fatty acid moieties of membrane phospholipids is a commonly observed phenomenon in a number of bacterial systems. The cyclopropane fatty acids are usually synthesized during and after the transition from exponential growth to stationary phase, or under such environmental conditions as acidic culture pH, low oxygen tension or high salt concentrations. S-Adenosylmethionine, the ubiquitous methyl group donor, provides the methylene bridge carbon in the reaction catalyzed by cyclopropane fatty acid synthase. Also formed in the reaction is S-adenosylhomocysteine, a potent inhibitor of cyclopropane fatty acid synthase, which is degraded by S-adenosylhomocysteine nucleosidase. This work provides evidence for at least two modes of regulation of lactobacillic acid synthesis, the cyclopropane fatty acid formed from cis-vaccenic acid (cis-11,12-octadecenoic acid), in Lactobacillus piantarum.

This work presents the development of a new highly sensitive and selective chemical assay for poly(ADP-ribose) which is routinely useful for the determination of polymer levels in vivo. This method was used to carefully measure poly(ADP-ribose) levels in normal and in DNA-damaged cells. The results of these studies strongly suggest that synthesis of poly(ADP-ribose) is involved in some aspect of DNA repair. A review of the literature is presented in the introduction of this work. Poly(ADP-ribose) synthesis has been implicated in aspects of transcription, in DNA syn thesis, and in DNA repair largely based on evidence from in vitro studies. It is apparent that current methodology has not allowed the routine quantification of poly(ADP-ribose) in vivo, hence the lack of i^n vivo data concerning the function(s) of the polymer. The body of this work presents the development of two chemical methods for the quantification of poly(ADP-ribose) and the application of one of these methods to the measurement of polymer levels in normal and DNA-damaged cells. Preliminary studies are presented on the utilization of combined gas chromatography/mass spectroscopy for the selective quantification of nucleoside derivatives. A second method makes use of the unique chemistry of the polymer for quantification. The polymer …

The glyoxalase system, which has been known since 1913, is widely distributed in nature. The system consists of two enzymes, glyoxalase I and glyoxalase II. Methylglyoxal is very unstable and undergoes oxidation and polymerization reactions. One of the purposes of this study was to find a simple, convenient and reproducible method of methylglyoxal preparation. Another objective was the purification of both glyoxalase enzymes employing affinity chromatography as a major step. The purified enzymes were to be characterized by chemical, physical and kinetic properties as an approach to the understanding of the biological function of the system.

This investigation is concerned with determining whether a carbon substituent or a silicon substituent on the carbon terminus of a silicon-carbon double bond has a more stabilizing effect. Two different 2-substituted silaethylenes were generated at the same time by pyrolyzing 1, 1-dimethyl-2-neopentyl-4- (dimethylalkoxysilyl) silacyclobutanes in a nitrogen flow system. The results of these pyrolyses, both neat and in the presence of a trapping reagent, show that the silaethylene with a silicon substituent on the carbon terminus was favored approximately two to one over the silaethylene with a carbon substituent. This datum, along with other observations and hypotheses discussed, leads to the suggestion that the silicon substituenton the carbon terminus of the silaethylene bond has a more stabilizing effect than the carbon substituent.

The synthesis and insecticidal activity of a series of 2,2-dicyano cyclopropane carboxylic acids, (3-phenoxyphenyl)- methyl esters were investigated. Synthesis of the compounds was accomplished by reaction of a dimethyl sulfonium carbethoxy ylide with propanedinitrile alkylidene compounds. Final products were formed in one step by use of the (3-phenoxyphenyl)-methyl ester of the ylide. Insecticidal activity was determined at 500 ppm application with Permethrin as the standard against houseflies, mexican bean beetles, and southern army worms.

A new approach was taken in the elucidation of the stereochemistry of the symmetrically 1,4-disubstituted 1,4-dihydronaphthalene systems which show deceptively simple NMR spectra. Thus, the stereochemistry of 1,4-di-tert-butyl-1,4-dihydronaphthalene was established unequivocally. The epoxide derivative, the subject compound, 1,4-di-tertbutyl-2, 3-epoxy-1, 4-dihydronaphthalene, was formed and its trans stereochemistry was established by ¹H NMR and ¹³C NMR. A lanthanide shift study was also conducted on the epoxide derivative, further proving the trans stereochemistry. One of the lanthanide shifted spectra was analyzed using the LAACOON III computer program and the true coupling constants obtained this way were in excellent agreement with the experimental spectrum. Establishing the trans stereochemistry of the epoxide derivative proved the trans stereochemistry of 1,4-di-tert-butyl-1,4-dihydronaphthalene.

A new, efficient route was used in the synthesis of [2.2]-paracyclophane-2-carboxylic acid. The acid as then resolved and the Birch reduction performed yielding one enantiomer of tetrahydro-[2.2]-paracyclophane-2-carboxylic acid. The ultraviolet spectrum of tetrahydro-[2.2]-paracyclophane- 2-carboxylic acid in isopenthane shows one absorption at 206 nm (Emax = 5,271). There are three bands observed in the circular dichroism spectrum in isopentane at 236 nm ([] = 1.8 X 104), 201 nm ([0] = -16 X 104) and a positive band indicated below 180 nm but not observed. The bands were assigned and possible reasons for the occurrence of a mr'r* transition at unexpectedly long wavelengths are discussed.

Two adsorption/microcoulometric methods have been investigated for total organic halogen (TOX) in water. TOX, a proposed water-quality parameter, is a rapid, surrogate method to detect halides microcoulometrically and does not require compound identification before water quality can be judged. An XAD resin is used to concentrate organic halides that are eluted by a two-step, two-solvent procedure, followed by analysis using :chromatography or pyrolysis to convert organic halides to halide. In the granular activated carbon (GAC) method, the entire GAC-organic halide sample is pyrolyzed. TOX measurements of model compounds are comparable by both methods, but GAC was found to be superior to XAD for adsorption of chlorinated humics in drinking water and chlorinated lake water.

The purpose of this investigation was to study the chemistry of the new and novel (trimethylsilyl)ketene. This ketene was synthesized by pyrolysis of (trimethylsilyl)ethoxyacetylene which was prepared from ethoxyacetylene and methyllithium. (Trimethylsilyl)ketene is a very stable and isolable ketene which does not dimerize and, therefore, provides an opportunity for some unique studies that have not been possible with other monosubstituted ketene.

The purpose of this investigation is to examine reactions of anions of oximes, oxime ethers and imines with acylating agents and other electrophiles. It is also an attempt to utilize the phenomenon of geometrical enantiomeric isomerism, in which absolute configuration is determined by double bond geometry, and the concept of regiospecific anion formation, also determined by double bond geometry, for stereospecific synthesis of tropinone derivatives.

The induced circular dichroism (ICD) of several chiral nitrosamines and various chiral reagents has been investigated. The interaction is attributed to a 1:1 hydrogen bonded complex between the NO group of the nitrosamine and the hydroxyl groups of alcohols and polyols, or the amino group of amines. Only those chiral reagents possessing large differences in size of the groups about the hydrogen bonding site contributed to CD anomalies. The acyclic 2-octanols did not give observable Cotton effects, presumably due to the similarity in size of the methyl and methylene groups and rotational freedom of the acyclic system. The signs of the Cotton effects could be correlated with the absolute configuration of the sterically hindered alcohols and amines. Only the alpha, axial hydrogens of conformationally biased, heterocyclic nitrosamines were found to undergo selective hydrogen-deuterium exchange, suggesting that this feature is critical for nitrosamine carcinogenicity.