<p>This dissertation focused on the development of mass spectrometric methodologies, separation techniques, and engineered devices for the optimal analysis of complex mixtures relevant to the energy sector, such as alternative fuels, petroleum-based fuels, crude oils, and processed base oils. Mass spectrometry (MS) has been widely recognized as a powerful tool for the analysis of complex mixtures. In complex energy samples, such as petroleum-based fuels, alternative fuels, and oils, high-resolution MS alone may not be sufficient to elucidate chemical composition information. Separation before MS analysis is often necessary for such highly complex energy samples. For volatile samples, in-line two-dimensional gas chromatography (GC×GC) can be used to separate complex mixtures prior to ionization. This technique allows for a more accurate determination of the compounds in a mixture, by simplifying the mixture into its components prior to ionization, separation based on mass-to-charge ratio (<i>m/z</i>), and detection. A GC×GC coupled to a high-resolution time-of-flight MS was utilized in this research to determine the chemical composition of alternative aviation fuels, a petroleum-based aviation fuel, and alternative aviation fuel candidates and blending components as well as processed base oils.</p> Additionally, as the cutting edge of science and technology evolve, methods and equipment must be updated and adapted for new samples or new sector demands. One such case, explored in this dissertation, was the validation of an updated standardized method, ASTM D2425 2019. This updated standardized method was investigated for a new instrument and new sample type for a quadrupole MS to analyze a renewable aviation fuel. Lastly, the development and evaluation of a miniaturized coreflood device for analyzing candidate chemically enhanced oil recovery (cEOR) formulations of brine, surfactant(s), and polymer(s) was conducted. The miniaturized device was used in the evaluation of two different cEOR formulations to determine if the components of the recovered oil changed.

Fungus Gloeophyllum trabeum (Agaricomytes: Gloeophyllates) is a brown rot wood-decay fungus which produces a vast spectrum of volatile secondary metabolites. Scientific publications state, that one of the metabolites produced by G. trabeum, can be the substance (3Z,6Z,8E)-dodecatrien-1-ol. This chemical substance is also the main component of trail-following pheromone of Rhinotermitidae termite family. In this diploma thesis, I was trying to verify whether various species of G. trabeum are in fact capable of producing the substance (3Z,6Z,8E)-dodecatrien-1-ol. I was also focusing on the effects of saccharides, present in nutrient solutions, on quantitative and qualitative change in composition of volatile secondary metabolites produced by G. trabeum. The saccharides I used for my research were - maltose, fructose, sucrose, xylose, and mannose. The analysis was made by using comprehensive two-dimensional gas chromatography separation technique with time-of-flight mass spectrometric detection (GC×GC-TOFMS). During my research I discovered that one of obtained species of G. trabeum can produce substance (3Z,6Z,8E)-dodecatrien-1-ol, but only under specific conditions. It is produced when cultivating on Petri dishes on agar - cellulose growth media. The measurement was further validated by...

In the first part of the doctoral thesis, the capillary electrophoresis was used to test the potential chiral separation properties of monosubstituted cyclodextrin derivatives, namely PEMEDA- and PEMPDA-β-cyclodextrins for the group of selected analytes. Both selectors exhibited excellent enantioseparation properties for N-boc-D,L-tryptophan, where the enantiomers were completely separated even at 0.5 mmol·l-1 concentration of the cyclodextrin derivative in the background electrolyte. However, the differences between the enantiodiscrimination properties of individual derivatives were minimal. The second test group consisted of two cyclodextrin derivatives, namely 2-O- and 3-O- cinnamyl-α-cyclodextrins. These derivatives are able to form supramolecular polymers in aqueous solutions that disintegrate at elevated temperature. The formation of these polymers was tested by NMR and DLS experiments. None of the tested cyclodextrin derivatives showed enantiodiscrimination properties towards a group of selected analytes. In the frame of antipredatory study, HPLC-MS/MS method working in HILIC mode was used for separation of ten pterin derivatives and riboflavin, which can be present as pigments in insects, reptiles or amphibians as a part of their warning coloration. The developed methodology was applied for...

<p>Technology has become increasingly more prevalent in all aspects of society since the age of the computer. The United States Military has successfully integrated the powerful processing capabilities of computers to increase the proficiency and lethality of its Soldiers, Sailors, Marines, and Airmen. However, this increased lethality comes at risk due to the inherent vulnerabilities of computer systems to spyware, malware, and counterfeit components. Inspired by the ability of canines to seek out and find electronic devices, this research sought methods to characterize components by their “scent” using precise analytical tools. Using these tools, this thesis sought to develop and utilize non-invasive methods to show proof-of-concept for electronic device classification by volatile compounds unique to different types of components. The findings of this research proved that electronic components that vary by age, origin, type, or manufacturer emit different volatile compounds available for detection using modern two-dimensional gas chromatography and solid-phase microextraction technologies. If developed further, the methods used in this research have the potential for application in the United States Department of Defense to ensure that all electronic components installed in their systems are authentic, come from a trusted source, and can be relied upon in even the most stressful operating conditions.</p>