Here, for the first time, the formation of adenine, hypoxanthine, and guanine from formamide solutions with heating only to 130 degrees C and UV-irradiation in the absence of minerals or inorganic salts is shown using LC-MS/MS as the analysis technique. The thesis goes on to demonstrate that the product distributions change drastically when the temperature is increased to 160 degrees C from 130 degrees C, specifically that the amount of hypoxanthine increases with the addition of UV light, and the amount of adenine increases with an increase in temperature. Along with showing the formation of purines in these reactions, the identification of pyrimidines was also achieved by GCxGC-MS. GCxGC-MS was also used to study additional samples, specifically bio-oils, where the type of compounds in the samples were easily identifiable, which allowed for a direct comparison between different types of bio-oils (e.g. Douglas-fir bark, Southern pine bark, and a Southern pine bark-wood mixture).

Sphingolipids are a highly diverse category of compounds that serve not only as components of biologic structures but also as regulators of numerous cell functions. Because so many of the structural features of sphingolipids influence their biological activity, there is a need for comprehensive methods for quantitation of as many individual subspecies as possible. This dissertation describes methods that have been developed and validated for the extraction, liquid chromatographic separation, identification and quantitation of sphingolipids by electrospray ionization (ESI), tandem mass spectrometry (MS/MS) using an internal standard cocktail developed by the LIPID MAPS Consortium. The compounds that can be readily analyzed are sphingoid bases and sphingoid base 1-phosphates, as well as more complex species such as ceramides, ceramide 1-phosphates, sphingomyelins, and mono- and di-hexosylceramides. For broader utility, the methods have been optimized for two categories of tandem mass spectrometers. With minor modifications, these methods can be applied to the analysis of isomers such as glucosylceramide and galactosylceramide, and with the availability of additional internal standards, more complex species such as sulfatides can also be quantified. Using these methods 46 species of these compounds have been quantified in RAW264.7 cells, a macrophage cell line. Quantitation of individual sphingolipid metabolites is possible using liquid chromatography, tandem mass spectrometry, and stable isotope labeling with [13C]palmitic acid can be used to differentiate between metabolites produced by de novo synthesis versus turnover. This approach is more accurate when one knows the isotope enrichment of the precursor pool (in this case, [13C]-palmitoyl-CoA); therefore this dissertation describes methods to analyze both the various isotopic forms of palmitoyl-CoA and sphingolipids through sphingomyelins and monohexosylceramides using two cell models, HEK293 cells and RAW264.7 cells treated with Kdo2-Lipid A. The sphingolipid analysis was simplified by the fragmentation of most of the metabolites to backbone product ions. For example the presence of the isotopic label in the long chain base, N-acyl linked fatty acid, or both was determined via, m/z 264 for [12C]sphingosine (d18:1) and m/z 280 for [13C]sphingosine (m+16, d18:1), versus the m/z of the isotopically labeled precursor, (m+16 versus m+32).

As concerns mount about the rise in atmospheric CO₂ concentrations, many different routes to reduce CO₂ emissions have been proposed. Of these, post-combustion CO₂ capture from coal-fired power stations is often the most controversial, as the CO₂ capture system will remove generating capacity from the grid whereas many of the other solutions involve increasing the generating capacity of the grid with low CO₂-emission plants. Despite this, coal-fired power stations represent a major point source for CO₂ emissions, and if a consensus is reached on the need to reduce CO₂ emissions, a low-cost method for capturing and storing the CO₂ released by these power plants needs to be developed. The overarching goal of this research is to design and develop a novel hollow fiber sorbent system for post-combustion CO₂ capture. To achieve this goal, three objectives were developed to guide this research: i) develop a conceptual framework for hollow fiber sorbents that focuses on the energetic requirements of the system, ii) demonstrate that hollow fiber sorbents can be created, and a defect-free lumen layer can be made, iii) perform proof-of-concept CO₂ sorption experiments to confirm the validity of this approach to CO₂ capture. Each of these objectives is addressed in the body of this dissertation. Work on the first objective showed that fiber sorbents can combine the energetic advantages of a physi-/chemi-sorption process utilizing a solid sorbent while mitigating the process deficiencies associated with using solid sorbents in a typical packed bed. All CO₂ capture technologies--including fiber sorbents--were shown to be highly parasitic to a host power plant in the absence of effective heat integration. Fiber sorbents have the unique advantage that heat integration is enabled most effectively by the hollow fiber morphology: the CO₂-sorbing fibers can behave as "adsorbing heat exchangers." A dry-jet, wet-quench based hollow fiber spinning process was utilized to spin fibers that were 75wt% solid sorbent (zeolite 13X) and 25wt% support polymer (cellulose acetate). The spinning process was consistent and repeatable, allowing for production of large quantities of fibers. The fibers were successfully post-treated with an emulsion-based polymer (polyvinylidene chloride) to create a defect-free lumen side coating that was an excellent barrier to both water and gas permeation. A film study was conducted to elucidate the dominant factors in the formation of a defect-free film, and these factors were used for the creation of defect-free lumen layers. The work discussed in this thesis shows that the second objective of this work was definitively achieved. For the third objective, sorption experiments conducted on the fiber sorbents indicated that the fiber sorbents CO₂ uptake is simply a weighted average of the support material CO₂ uptake and the solid sorbent uptake. Furthermore, kinetic experiments indicate that CO₂ access to the sorbents is not occluded noticeably by the polymer matrix. Using the fiber sorbents in a simulated rapid thermal swing adsorption cycle provided evidence for the fiber sorbents ability to capture the sorption enthalpy released by the CO₂-13X interaction. Finally, a slightly more-pure CO₂ product was able to be generated from the fiber sorbents via a thermal swing/inert purge process.

Thesis (Ph. D.)--University of Hong Kong, 2001. / Includes bibliographical references.

Thesis (Ph. D.)--Institute of Paper Chemistry, 1975. / Includes bibliographical references (p. 94-100).

Thesis (Ph. D.)(Chemistry)--University of Pretoria, 2003. / Includes bibliographical references.

Thesis (Ph.D)--Biology, Georgia Institute of Technology, 2009. / Committee Chair: Alfred H. Merrill, Jr; Committee Member: John Cairney; Committee Member: M. Cameron Sullards; Committee Member: Marion B. Sewer; Committee Member: Yuhong Fan. Part of the SMARTech Electronic Thesis and Dissertation Collection.

Chemical enhanced oil recovery (CEOR) has gained a rapid momentum in the recent past due to depleting reserves of “easy-oil” and soaring oil prices. Hence, CEOR is now being considered for several candidates with varied oils and reservoir conditions, which demands the need for large hydrophobe surfactants. A new class of thermally and chemically stable large hydrophobe surfactant, Guerbet alkoxy carboxylates (GAC) has been tested. Unlike Guerbet alkoxy sulfates, GAC are stable at all pH and can be extremely useful in cases where alkali usage is prohibitive. They also exhibit synergistic behavior with internal olefin sulfonates (IOS) and alkyl benzene sulfonates (ABS), with the mixture showing enhanced calcium tolerance than the individual surfactants. Furthermore, in an attempt to diversify the raw material base, a new class of hydrophobe, viz. tristyrylphenol (TSP) based on petrochemical feed stock has also been developed and evaluated. Given the fact that there are hundreds of surfactants that can be tested for a particular candidate, the difficulty often lies in choosing the right surfactant to begin with. In an attempt to simplify that, a new correlation to predict the optimum surfactant structure has been developed. It relates the optimum surfactant structure to the formulation variables like oil properties, salinity, and temperature, including the parameters like PO and EO for new-generation surfactants. The correlation can serve as a guideline in choosing the optimum surfactant and will help in improving our understanding of the relationship among variables affecting the optimum surfactant structure. Surfactant retention is an important factor affecting the economics of chemical flooding and has to be studied carefully. Using an extensive data obtained from core flood studies a new correlation for predicting surfactant retention including the variables like pH, TAN, salinity, mobility ratio, temperature, co-solvent, and surfactant molecular weight has been developed. All these are new and highly significant advance in the optimization of chemical EOR processes that will greatly reduce the time and cost of the effort required to develop a good formulation as well as to improve its performance. / text

M. Tech. Chemistry. / Investigates the methods of preparing verbascoside-rich plant extracts, identifying viable sources of the compound and evaluating its stability under various conditions. Leaf extracts of Lippia javanica and Lantana camara (Verbenaceae) were partially purified using column chromatography and high speed centrifugal countercurrent chromatography.

M. Tech. Chemistry. / Aims to evaluate, compare and modify existing methods and investigate new methods for the qualitative and quantitative determination of melamine. Specific aims were to: evaluate and modify an existing GC-MS15 and HPLC-DAD method16, published by US FDA, for the determination of melamine in pet food and baby milk powder formulae ; develop a novel HPLC fluorescence detection (FLD) method for the determination of melamine in pet food and baby milk powder formulae ; compare these methods to a commercial ELISA detection method for the determination of melamine in pet food samples previously implicated in the poisoning of dogs ; apply NIR spectroscopy with subsequent multivariate analysis to rapidly determine melamine in pet food; and compare the different methods statistically with respect to their analytical performances.