Thesis (Ph.D.)--McMaster University, 2005. / Supervisor: John F. Valliant. Includes bibliographical references. Also available online.

Thesis (M.S.)--Florida State University, 2004. / Advisors: Dr. Jeffrey Chanton and Stephen Opsahl, Florida State University, College of Arts and Sciences, Dept. of Oceanography. Title and description from dissertation home page (viewed Jan. 13, 2005). Includes bibliographical references.

Thesis (Ph.D.)--Hong Kong University of Science and Technology, 2004. / Includes bibliographical references (leaves 247-267). Also available in electronic version. Access restricted to campus users.

The traditional approach for predicting the risk of hydrophobic organic contaminants in sediment is to relate organic carbon normalized sediment concentrations to body residues or toxic effects in organisms. This method is limited, however due to the plethora of variables that can influence bioavailability. Therefore, a matrix independent method of predicting bioavailability needs to be developed in order to be universally applicable. Solid phase microextraction (SPME) and Tenax are two commonly used bioavailability-based methods. While both SPME fiber and Tenax extractable concentrations can be correlated to tissue residues of aquatic species, the majority of this research (with a few exceptions) focuses on compounds that are not acutely toxic or biotransformed. Less is known about the potential applicability of these methods to predict bioaccumulation, and ultimately toxicity, for highly toxic, rapidly biotransformed compounds, such as pyrethroid insecticides. This class of compounds is of particular concern due to frequent environmental detection in sediments at concentrations lethal to benthic species. This research has four specific goals: Determining exposure conditions that may change the concentration on the SPME fibers at equilibrium (Chapter 2); Comparing the ability of SPME fibers and Tenax to predict the bioavailability of two pyrethroids (permethrin and bifenthrin) (Chapter 3); Developing bioavailability-based toxicity endpoints for bifenthrin using two aquatic species (Chapter 4); and, Validating these techniques using sediments from known contaminated field sites (Chapter 5). Overall this research was focused on comparing and contrasting the ability and applicability of SPME fibers and Tenax to adequately predict the exposure of pyrethroids under varying conditions. While comparing these two methods, they were optimized to better provide accurate predictions of bioavailability and toxicity for pyrethroids from sediments. Regardless of the fiber or animal density examined, the SPME fibers exposure did not significantly affect fiber concentrations for permethrin or DDE. Additionally, bioaccumulation of parent permethrin and bifenthrin was predicted using both SPME fibers and Tenax using 6 or 24 h extraction times. Further, a single regression model predicted bioaccumulation across compounds and species using Tenax extractable concentrations. Once demonstrated that these techniques could predict bioaccumulation, median lethal and effect levels were examined for bifenthrin and as expected the bioavailability-based endpoints were more uniform across sediments than use of whole sediment concentrations. Additionally, the relationships among the two methods were compared across multiple sediments. Despite the SPME fiber's ability to determine toxicity in laboratory sediments, the field validation study determined that lethal levels were often too low to detect on the SPME fibers using current methodologies, but Tenax extractable concentrations correlated to toxicity. Overall, while both methods could predict bioavailability, the limitations of SPME fibers including lower sensitivity, inability to function across compounds, and long equilibration time, made Tenax extraction a preferable method.

The use of SiGe/Si heterostructures in the fabrication of electronic devices results in an improvement of the device performances with respect to bulk silicon. Ion implantation has been proposed as one of the possible technologies to produce these structures and, thus, the aim of this work is to develop an ion beam technology to fabricate strained SiGe heterostructures. The formation of extended defects in SiGe alloy layers formed by high dose Ge+ ion implantation followed by Solid Phase Epitaxial Growth (SPEG) has been investigated by transmission electron microscopy. Rutherford backscattering spectroscopy has also been used to determine the chemical composition and the crystalline quality of the synthesised structures. In addition, X-ray diffraction has been used to evaluate the strain level in selected samples. Two different structures have been studied in this project. The first consisted of "all-implanted" layers, where the Ge+ implants were followed in some cases by additional implants of Si+ and/or C+ ions, prior to SPEG, to investigate methods to inhibit defect formation. The second was achieved by capping the ion beam synthesised SiGe alloy layer by the deposition of a thin film of silicon, in order to realise structures compatible with device dimensions. Single crystal device worthy SiGe alloy layers have been achieved by implantation of Ge+ ions at energies ranging from 70 keV to 400 keV, where the only extended defects observed are EOR defects at a depth correspondent to the a/c interface formed during the Ge+ implant. In some cases, "hairpin" dislocations have also been observed in the vicinity of the EOR defects and extending up to the surface. Both types of defects are annihilated after post-amorphisation with 500 keV Si+ and replaced with dislocation loops at a depth of about 1 fj,m. For each Ge+ implantation energy a critical value of the peak germanium concentration exists above which the structures relax through the formation of stacking faults or "hairpin" dislocations nucleated in the vicinity of the peak of the germanium concentration depth profile and extending up to the surface. A critical value of the elastic energy stored in the structures (~300 mJ/m2) has been determined above which ion beam synthesised SiGe alloys relax, independently of the implantation energy. This empirical approach has been found to successfully account for the results obtained in this work as well as in many other studies reported in the literature. "Hairpin" dislocations formed under different experimental conditions have been investigated by plan view TEM and have been found to have the same crystallographic orientation () and Burgers vector (b= a ). Their formation has been explained within a "strain relaxation model". For a regrowth temperature of 700° C, all samples investigated by XRD have been found to be almost fully strained, including samples containing relaxation-induced defects, indicating that, under these conditions, the energy transferred to the defects is very low. C+ co-implantation has been successfully used to reduce both relaxation-induced defects and EOR dislocation loops. It is noted that a mixed technology entailing both layer deposition and ion implantation to produce the Si/SiGe/Si device structures requires extra process steps to control surface contaminations, pre cleaning and/or native oxide formation, resulting in increased fabrication costs. In this work an " all-implanted" route to the synthesis of Si/SiGe/Si device structures is therefore described, which exploits all of the advantages given by ion implantation.

Thesis (M.S.)--State University of New York at Binghamton, Department of Chemistry, 2006. / Includes bibliographical references.

Indiana University-Purdue University Indianapolis (IUPUI) / A novel route has been developed for the solid-phase synthesis of N-carboxyalkyl unnatural amino acids as potential metalloprotease inhibitors. The key step involves a nitrogen alkylation of resin-bound amino acids with -bromoesters. Alkylation of the benzophenone imine of glycine on Wang resin was used to introduce unnatural amino acid side chains onto the resin-bound glycine. The benzyl -bromoesters [BrCH(R2)CO2Bn], starting materials for the C-N bond construction, were prepared in solution by diazotization of naturally-occurring amino acids to form the -bromoacids, followed by benzylation of the carboxylic acid to form the benzyl -bromoesters. N-Alkylation of the resin-bound, unnatural amino acids with the benzyl -bromoesters and subsequent cleavage from resin gave the benzyl ester monoacid intermediates. Exploration of reverse-phase cyano-silica gel chromatography and preparative liquid chromatography provided effective purification of the benzyl ester intermediates. Hydrolysis of the analytically pure benzyl ester monoacids afforded clean products as the diacids. The two points of variation introduced through the two on-resin alkylation steps, C-alkylation of the benzophenone imine of glycine and N-alkylation with the benzyl -bromoesters, allow for the combinatorial synthesis of a library of target compounds.

This thesis describes the synthesis, characterisation and coordination chemistry of a variety of fluorinated ß-diketonate ligands (I) and carboxylate ligands (II), the catalytic activity of the resultant metal complexes for oxidation and C-C bond forming reactions, and an evaluation of fluorous methodologies for catalyst/product separation. (Fig. 3706) Chapter 1 introduces the concept and application of fluorous methodologies, including fluorous biphase catalysis and fluorous reverse phase silica gel (FRPSG), as alternative approaches to product/catalyst separation in homogeneous catalysis. Chapter 2 describes the synthesis and characterisation, in some cases by X-ray diffraction, of the fluorinated ß-diketonate ligands and an evaluation of the influence of the perfluoroalkyl groups on the coordination of these ligands to a variety of transition metals including copper, nickel, palladium and zinc. Chapter 3 outlines attempts to sue fluorous nickel ß-diketonate complexes for the oxidation of sulfides. The results indicate that a metal catalyst is not necessary for oxidation in this system although the veracity of catalyst separation using FRPSG was established. This chapter also describes the investigation of a fluorous molybdenum ß-diketonate complex for the oxidation of alkenes, although the extreme moisture senstiviity of the complex negated any attempts at recovery and recycling. The scope of Lewis acid catalysed coupling of ß-diketones with cyanoformates and the ability to reuse and recycle the fluorinated ß-diketonate catalysts is described in chapter 4. Chapter 5 describes attempts to extend this efficient separation procedure to the C-C bond forming reactions of rhodium carboxylate dimers. Although catalysis was observed, catalyst/product separation using FRPSG was unsuccessful. Chapter 6 summarises all the experimental details and spectroscopic data, whilst a CD-rom includes all of the crystallographic data.

This thesis project describes research using headspace solid phase micro-extraction with gas chromatography (HS-SPME GC-MS) as an analytical tool for assessing textile fibres. It was found that this method required a temperature of >500oC to pyrolize the textile sample. A total of 5 minutes was determined to be the optimal time for collecting the volatile analytes. Numerous analytes were found to be chemical markers for each of the individual textile fibres. The chemical markers are qualitatively used to describe each textile uniquely, and it was found that by using the chromatographic patterns, the textiles could be identified individually and in mixtures containing two textiles. Lastly, by accelerating the age of the textile fibres by means of heat, ultra-violet light, and humidity, a comparison was made between the un-aged and aged fibres. It was found that each of the techniques arose different results and in some cases new compounds. / October 2016

In the field of forensic toxicology, several challenges exist with quantification analysis of cocaine and metabolites in post mortem samples. Cocaine can prove difficult to detect and quantify in blood, urine, and soft tissues following extensive decomposition. Alternative matrices, such as hair, nails, and bone could prove useful in detecting chronic drug use in post-mortem toxicology cases. Detection and quantification of drugs in complex matrices is difficult to accomplish due to time-consuming extraction processes, and inability to detect an analyte at trace levels. Further, analysis of drugs in hard tissues, such as hair and bone, has only been attempted in recent years. Even fewer studies have investigated detection of drugs following decomposition of remains, specifically outdoor decomposition. The objective of this study was to develop a robust extraction and clean up methodology, in which a homogenization step precedes, to efficiently extract drugs from complex matrices, reach a target limit of detection (LOD) and to maintain instrument performance using multidimensional chromatography. Multi-dimension chromatography platform such as two dimensional liquid chromatography tandem mass spectrometry ( 2D-LC/MS/MS,) offers options not compatible with single dimension v units. With large volume injection capabilities of aqueous and organic extracts, the analytical process be reduced from multiple hours to minutes. All rat specimens used for this study fell under an Institutional Animal Care and Use Committee (IACUC) protocol. The rodents underwent a 10-12 weeks chronic intravenous self-administration of cocaine. This was followed by a six-week period of abstinence, followed again by a three-week period of cocaine self-administration before being euthanized. Average daily dosages for each rat fell within a range of 13-19 mg/kg. A total of 14 cocaine positive rats were placed outside and above ground in the Boston University Forensic Anthropology Outdoor Research Facility (Holliston, MA, U.S.A) for a period of 12 months. All recoverable skeletal samples were collected for testing. Drug free control rat bones were also acquired by placing drug-free rats outdoors, above ground, until full decomposition occurred. In this study, a method analyzing cocaine and its major metabolites benzoylecgonine and ecgonine methyl ester was developed. After homogenization of whole bones, the extraction process was performed using a mixed mode reversed-phase/ion exchange sorbent. The use of a 2D LC/MS/MS technology eliminates the need for a lengthy evaporation step in the extraction method. The chosen 2D LC/MS/MS used in this application was identified using a 6x6 automated method development protocol. The manual extraction of the bone samples was completed in less than an hour. The analysis was performed using 100μL of the final organic solvent (MeOH) extracts. vi The limit of quantitation (LOQ) for cocaine and benzoylecgonine was measured at 0.05ng/g (0.05ng/mL or 50pg/g) of sample material and the LOQ for ecgonine methyl ester was measured at 0.1ng/g (0.1 ng/mL or 100pg/g). The extraction method for cocaine proved to give a linear dynamic range of 2.5 orders of magnitude (0.05 ng/g to 10ng/g with an R2 = 0.998. The micro extraction protocol combined with a multi-dimension chromatography used in this study decreased sample preparation time without sacrificing the quality seen with current single dimension chromatography techniques. The procedure developed in this study can be utilized on bone and completed in less than an hour before injection into the 2D-LC/MS/MS system.