Thesis (Ph. D.)--University of Washington, 2004. / Vita. Includes bibliographical references (leaves 186-201).

Thesis (Ph. D.)--Carleton University, 2000. / Also available in electronic format on the Internet.

Thesis (Ph. D.)--University of Washington, 2005. / Vita. Includes bibliographical references (leaves 201-237).

This dissertation describes the results of time-of-flight spectroscopic examination of H⁺ ions resulting from electron bombardment of the hydrogen halide molecules HF, HCl, HBr, and HI. The time-of-flight spectra of the H⁺ fragments and their corresponding H⁺ fragment kinetic energy spectra are used to study the dissociative processes that yield H⁺ fragments for electron bombardment energies in the 15 eV to 51 eV range. The H⁺ fragments are produced in an interaction region defined by a pulsed electron beam colliding with the target gas. By keeping the gas pressure sufficiently low to guarantee that the fragment path length to the ion detector is much less than the mean-free path length in the gas, the fragments' velocities can be considered a sample of fragment velocities produced by the electron beam and hydrogen halide gas in the interaction region. The geometry of the interaction region primarily detected fragments produced at 90° to the electron beam axis. The electron gun used was designed to allow computer control of the electron bombardment energy. The computer also controlled a programmable multichannel analyzer that allowed the data to be acquired in a fashion that permitted normalization of the H⁺ TOF spectra taken at different electron bombardment energies. This normalization procedure allowed the use of ionization efficiency curves in detection of the thresholds of H⁺ production channels for HCl and HBr. For HF and HI the thresholds of H⁺ production channels had to be determined by visual examination of the TOF spectra. The electronic structure of the hydrogen halide molecules has been a popular topic of study over the years. Since this work represents the first TOF study of electronic excitation processes that lead to dissociation resulting in H⁺ fragments from the hydrogen halides, it should prove to be a significant contribution toward an understanding of the highly excited electronic states of these molecules and their molecular ions. The interpretation of the results obtained indicated that both configuration interactions between adiabatic electronic states that lead to predissociation-type processes and inner valence shell excitations were probably the primary contributors to the H⁺ fragment production.

Li Yiu-Ching. / Thesis (Ph.D.)--Chinese University of Hong Kong, 2001. / Includes bibliographical references (p. 123-132). / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Mode of access: World Wide Web. / Abstracts in English and Chinese.

The Centers for Disease Control and Prevention deemed the increase in overdose fatalities, due to the use of opioids, an “opioid epidemic” in the United States. Heroin, fentanyl, and other synthetic opioids are commonly abused and are contributing to the opioid epidemic. In 2016, the Drug Enforcement Administration temporarily placed three fentanyl analogs (beta-hydroxythiofentanyl, butyryl fentanyl, and furanyl fentanyl) under Schedule I due to their imminent threat to public health. These drugs elicit analgesic effects similar to heroin making them desirable drugs to abuse. Novel fentanyl analogs and designer opioids are expected to become more prominent in forensic casework in the near future as the opioid epidemic continues. These drugs can be seen in forensic seized drug and urine casework samples either alone or mixed with other drugs of abuse. It is therefore necessary to have an efficient methodology to identify these new compounds. Currently, gas chromatography-mass spectrometry (GC/MS) is used to identify drugs of abuse and is considered the “gold standard” in forensic casework. However, analysis times can often range from 15 to 60 minutes in length. Another drawback is the need for spectral library matching, which requires analytical reference materials for identification. Therefore, the identification of novel fentanyl analogs and designer drugs is limited until a reference material becomes available. In this study, direct sample analysis time-of-flight mass spectrometry (DSA-TOFMS) was evaluated to provide rapid identification of fentanyl and other synthetic opioids in seized drug and urine casework samples. DSA is a direct ambient ionization source, which requires no chromatography and minimal sample preparation. TOFMS is a high resolution mass spectrometer that uses collision-induced dissociation (CID) to produce precursor ion and characteristic fragmentation ions, which provide additional structural and molecular formula information, allowing for the identification of compounds without a reference material. The analytes explored in this study include: heroin, 6-monoacetylmorphine (6-MAM), morphine, fentanyl, norfentanyl, 4-anilino-N-phenethylpiperidine (4-ANPP), acetyl fentanyl, beta-hydroxythiofentanyl, butyryl fentanyl, furanyl fentanyl, valeryl fentanyl, AH-7921, U-47700, buprenorphine, norbuprenorphine, desomorphine, MT-45, W-15, and W-18. Direct sample analysis time-of flight mass spectrometry (DSA-TOFMS) is a novel instrumentation that could be utilized in the forensic sciences field to qualitatively identify illicit substances in casework samples. In this study, 19 compounds of interest containing heroin, fentanyl, fentanyl analogs, and other synthetic opioids were evaluated using DSA-TOFMS. DSA-TOFMS abbreviated the workload of the analysis and was utilized to provide precursor ion and characteristic fragmentation ions within an analysis time of 20 seconds. Certified reference standards were used to optimize instrumentation settings, to determine precursor ions and characteristic fragmentation ions, and to determine the limit of detection of the instrument. A carryover study determined there were no persisting ions present when entering the capillary inlet between runs. A repeatability study revealed the DSA-TOFMS repeated results within the acceptable criteria range of above 500 counts and within 10ppm error 93% (10ppm) and 83% (1ppm). Forensic seized drug casework samples were evaluated with DSA-TOFMS and qualitatively identified. Out of the 64 samples, 89% were qualitatively identified as heroin, 4% were qualitatively identified as fentanyl, 1% was qualitatively identified as heroin and fentanyl, 3% were qualitatively identified as acetyl fentanyl, and 3% were qualitatively identified as furanyl fentanyl. The casework samples containing furanyl fentanyl were considered “true unknown unknown samples,” as the Maine Health and Environmental Testing Laboratory gas chromatography-mass spectrometry library did not have a spectrum to use for the identification of these samples. Forensic urine casework samples were evaluated with DSA-TOFMS. Samples previously confirmed to contain compounds of interest were prepared using minimal sample preparation technique (filtered using 0.45 microns syringe filters and diluted (1:10) with LC/MS grade water). Analysis displayed the limitations of DSA-TOFMS as only twelve of the forty compounds of interest were present and only three of the twelve were within the acceptable criteria range. DSA-TOFMS is a fast and reliable technique with minimal sample preparation for forensic seized drug samples. However, the concentration in complex matrixes, such as urine and blood, were unable to be qualitatively identified using this sample preparation method by DSA-TOFMS.

In this thesis, we investigated the surface composition and orientation of both pure room-temperature ionic liquids (Ils) and binary mixtures of the ILs of the type consisting of the 1-alkyl-3-methylimidazolium ([C[subscropt n]mim]���, n=4, 8, and 12) cation coupled with either [PF���]���, [BF���]���, [Cl]���, or [Br]���. The surfaces of the ILs were examined using both direct recoil spectrometry (DRS) and surface tension measurements. With DRS, a spectral signal produced by a recoiled surface atom indicates the existence of a particular molecular or ionic species at the interface. Derived from the signal are the atomic ratios, which are strongly dependent on the surface orientation of the surface species. The DRS findings are complimented with surface tension measurements, and the thermodynamics properties (surface enthalpy and entropy) derived from such measurements are related to the surface composition and orientation. From the experiments on the neat ILs, the surface compositions of the imidazolium-based ILs were determined. Furthermore, the effects of systematic variations of the cation size (the length of the 1-alkyl chain) and anion identity on the surface orientation of the organic cation were also examined. The surfaces of binary mixtures containing ~25 mol % of [C������mim][PF���] or [C������mim][BF���] in [C���mim}[BF���] were also investigated. The DRS and surface tension data of the mixtures were compared to those of the pure components to determine the composition and any changes in the orientations of the cations upon mixing. / Graduation date: 2004

Thesis (Ph. D.)--University of Missouri-Columbia, 1999. / Typescript. Vita. Includes bibliographical references. Also available on the Internet.

Thesis (Ph. D.)--University of Missouri-Columbia, 1999. / Typescript. Vita. Includes bibliographical references. Also available on the Internet.

Thesis (Ph. D.)--West Virginia University, 2002. / Title from document title page. Document formatted into pages; contains ix, 99 p. : ill. (some col.). Includes abstract. Includes bibliographical references.