Thesis (Ph. D.)--Syracuse University, 2004. / Advisers: Nafie, Laurence A.; Freedman, Teresa B. "Publication number AAT 3149049."

Thesis (Ph. D.)--Syracuse University, 2004. / "Publication number AAT 3132726."

Thesis--Universiteit van Utrecht. / Bibliography: p. 101-104.

From Introduction: Wax and wax-like substances have been defined in many ways. One reasonably extensive definition, by Hatt and Lamberton (1956) is given below: "The term "wax" seems best used to denote a group of substances which qualitatively have certain physical properties in common. These properties are familiar ones, for in almost all countries some natural wax - beeswax, Japan wax, Chinese insect wax, the carnauba and candelilla waxes of the Americas - has been an important material in art and industry from prehistoric times. Waxes are understood to be opaque or translucent solids, which melt without decomposition to form mobile liquids at temperatures in the region of 100⁰C. They differ in hardness, but are all essentially soft substances with poor mechanical strength. Most waxes can be easily shaped or kneaded at a little above ambient temperatures. In fact, the term could easily have been made to cover the whole class now named thermoplastics." Pure n-paraffins would be too crystalline and brittle for use as waxes, whereas mixtures of n-paraffins have some valuable properties. The molecules bear such close resemblance to one another that they form mixed crystals of lowered crystallinity and the melting point is a function of the mean molecular weight. This is a desirable feature for it permits crystallinity and brittleness to be reduced without a marked loss in the melting point or hardness. It also allows a mixture to simulate a pure compound very closely. Waxes, in general, have been put to a large number of uses. They are used, for example, in candles, polishes, paper-coating, plastics, printing, matches, rust protectants and insulation. Each application requires its own appropriate range of wax properties.

Sequential injection has, over the past eight years, developed into a viable alternative to flow-injection, but its full potential has not yet been fully realized. It developed out of existing flow-injection methods when a need for mechanically simple and robust flow-injection methodology arose. In this study the development of this method is discussed with its numerous advantages and disadvantages over existing flow-injection methods. The theoretical basis on which this technique is based is outlined as well as parameters that influence the design of the manifold. With the manifold design principles established, the manifold is evaluated using real sample analysis, with liquid fertilizer as the source of selected elements. Adjustments made to existing flow-injection methods, for the determination of nitrite with sequential injection analysis, are discussed, while a new method is proposed for nitrate determination. The viability of solid-phase reductors and in situ preparation of reagents, combined with sequential injection analysis, is also studied. / Dissertation (MSc (Chemistry))--University of Pretoria, 2006. / Chemistry / unrestricted

Call number: LD2668 .T4 1952 M3 / Master of Science

A direct method for source determination of atmospheric formic and acetic acid, through carbon isotopic analysis of the ambient acids and their potential sources, has been successfully developed and tested. These first carbon isotopic measurements of formic acid in the atmosphere were found to be fairly constant, regardless of location. This is consistent with a single dominating source of formic acid, with vegetation emissions being the most likely controlling source. Collection of relatively large quantities (0.3$-$3.0 mg) of the organic acids, which was necessary for carbon isotopic measurements, was effectively accomplished by a new method using calcium hydroxide-treated filters with a high-volume sampler. Samples were collected on a regular basis at Mount Lemmon, Arizona (elevation = 9200 feet A.S.L.). Atmospheric concentrations showed a well-defined seasonal pattern, with the lowest concentrations (about 0.2 ppbv) occurring in the middle of the winter, which steadily increased to a maximum of nearly 2 ppbv in the summer. The ¹³C content (δ ¹³C) of HCOOH averaged -20.9 ± 2.5 ‰ during the growing season (April-September) and -23.2 ± 3.5 ‰ during the non-growing season at Mount Lemmon. Isotopic measurements of formic acid from several other locations included two west coast marine sites (δ ¹³C range of -19.1 to -24.6 ‰), three Colorado Rocky Mountain samples averaging -23.2 ± 1.0 ‰, two from the prairie of North Dakota (-23.5 ± 1.0 ‰) and three samples collected in the urban Tucson, Arizona area (-20.8 ± 3.4 ‰). Source measurements included HCOOH emissions from two species of formicine ants (-18.8 ± 1.7 ‰), and HCOOH in automobile exhaust (-28 ‰ from leaded gasoline, and -48.6 ‰ from unleaded). Further support for a biogenic source of atmospheric HCOOH came from the carbon-14 analysis of six Mount Lemmon HCOOH samples (93-113% modern carbon), using accelerator mass spectrometry. Carbon isotopic fractionation during exchange of HCOOH between the liquid and gas phases was investigated through a gas/liquid partitioning experiment. A first experimental measurement of the Henry's Law coefficient (Kᴴ) averaged 7400 ± 800 M/atm. Fractionation between HCOOH(g) and HCOOH(aq) was found to be negligible.

The overall goal of this research is to characterize the potential-dependent structure and composition of the alcohol-Ag electrochemical interface. The approach involves the use of a variety of electrochemical and spectroscopic tools to arrive at a consistent model for a series of straight-chain alcohols (methanol, ethanol, 1-propanol, and 1-pentanol) at Ag electrodes. There are essentially four areas of investigation presented in this dissertation. The first portion of this work has been directed at the development of charge coupled device detection in Raman spectroscopy so that many of the interface investigations could be performed. The advantages and limitations of these detectors in Raman spectroscopy are addressed. The second area involves the characterization of in-situ alcohol-Ag electrochemical interfaces using Raman spectroscopy and associated surface selection rules for the evaluation of solvent orientation and bonding. Since the series of alcohols offers a systematic variation in solvent properties, these studies provide substantial insight regarding some of the chemical interactions which can dictate orientation. The development of emersed electrode technologies is also presented as a means to improve selectivity for surface molecular species over bulk molecular species. The utility of this approach is demonstrated for a variety of straight-chain alcohols at both rough and smooth Ag electrodes. Conditions for emersing the molecular interface, intact, under potential control are presented. Finally, double layer capacitance measurements are performed to offer additional insight regarding alcohol solvent structure and interfacial composition as a function of electrode potential. In addition, capacitance-potential plots are used along with the Hurwitz-Parsons analysis to determine absolute surface coverage of Br⁻ as a function of electrode potential. These results are correlated with the Raman spectroscopic results to obtain a consistent model for the structure and composition of the alcohol-Ag electrochemical interface.

The application of mass spectrometry to verification of the structure of 3-methyluridine (m³U) isolated by HPLC from normal human urine is described. m³U has been used as an internal standard for studies of urinary nucleosides, a practice that is discouraged with the confirmation of m³U as a naturally occurring compound. Mass spectrometry has been used for the identification of 5'-deoxyxanthosine (5'-dX) a novel nucleoside in normal human urine. Initial concern over availability of a reference sample of 5'-dX prompted investigations of the structure/fragmentation relationships of the TMS deratives of 2'-, 3'-, and 5'-deoxynucleosides toward differentiation between the three deoxynucleosides. Results are presented which allow discrimination between the model compounds, deoxyanalogs of adenosine. Subsequent to the deoxynucleoside fragmentation studies, a biosynthetically produced reference sample of 5'-dX became available for direct comparison of mass spectra and chromatographic retention times which, when combined with observations from the deoxynucleoside studies established the structure of 5'-dX. In response to the large number of mass spectra produced from the GC-MS analysis of a TMS derivatized urine sample, computer software has been written to aid in spectral analysis. Examples are shown in which the software uses established fragmentation rules to assign structure to ions in the mass spectrum and suggest modifications in the sugar portion of two urinary nucleosides. The structure/fragmentation relationships of the unique antitumor drug taxol has been studied by EI, CI and FAB mass spectrometry. Information is presented showing characteristic fragmentation of the side-chain and verification of functional groups attached to the taxane ring. Studies have been conducted to determine the relationship between target temperature and matrix and sample lifetime in the source of the mass spectrometer. Results are presented showing that cooling the target permits the use of matrix materials that are too volatile at ambient temperatures thus extending the range of compounds that can be studied by mass spectrometry. A recently constructed four-sector mass spectrometer is described with a detailed discussion of instrumental capabilities. Results of experiments designed to apply these capabilities to the structural analysis of TMS nucleosides using FAB ionization are discussed with an emphasis on the fragmentation unique to 4-sector daughter ion experiments compared with conventional studies and 2-sector daughter ion results.

A unique echelle spectrometer system employing charge injection device (CID) array detectors for use in inductively coupled plasma atomic emission spectroscopy (ICP-AES) is described. The echelle spectrometer described offers numerous advantages over previous systems including improved light throughput and extended wavelength coverage including the vacuum-ultraviolet (VUV) down to 165 nm. Several improvements in CID array detector technology are also described. Low exposure level linearity is improved and full well capacity is increased by fabricating the CIDs with <100> silicon as opposed to <111> silicon. Low sensitivity in the far-ultraviolet (far-UV) has been considered a major disadvantage when using silicon based detectors due to absorbance in the overlying gate structure of the devices. The problem has been circumvented by utilizing a wavelength conversion phosphor to improve the effective sensitivity in the far-UV. The read noise of the CID has been reduced by a factor of 3 by utilizing a preamplifier on every row of the device. Utilization of this system for ICP-AES yields numerous advantages over conventional photomultiplier tube (PMT) based systems. Elemental detection limits comparable to or better than those obtained on PMT based instrumentation are achieved in the UV and visible regions. Sensitivities at wavelength less than 200 nm are degraded by a factor of 5 relative to PMT based systems due to decreased echelle grating efficiency in that wavelength region. In most cases, the advantages of continuous wavelength coverage provided by CID array detectors outweighs any loss in sensitivity. Operating parameters including precision, resolution and background correction are also discussed. Analysis of both the National Institute of Standards and Technology (NIST) Standard Reference Materials (SRM) 1643b and 1646 demonstrates that the system is capable of the simultaneous determination of a large number of elements at a large number of wavelengths with a high degree of accuracy even in spectrally complex matrices.