Applications of chromatography, mass spectrometry, and spectroscopy for composition and trace analysis of polymeric and forensic samples

The first half of this manuscript focuses on characterization and analysis of polymeric samples using Py-GC/MS, MALDI MS, ATR-FTIR and statistics. The first two chapters present studies involving the elucidation of the fragmentation reactions, using Py-GC/MS and MALDI TOF/TOF MS, for two important industrial poly(aryl ether sulfone)s: polysulfone and poly(phenyl sulfone). The third chapter used the composition of the major pyrolysis products of Kraton 1107, a styrene-isoprene copolymer, and statistics to calibrate the set pyrolyzer temperature with the actual temperature experienced by the sample. This calibration method provides a practical technique for relating pyrolysis parameters between different systems. The fourth chapter used ATR-FTIR of poly(ethylene-co-vinyl acetate) and partial least squares (PLS) regression employing the entire IR spectrum to develop a quick, rugged method to quantitate the amount of vinyl acetate present.;The second half of this manuscript focuses on the analysis of forensically relevant samples. Chapter five involves the ATR-FTIR and linear discriminant analysis to discriminate between black electrical tapes. Chapters six to nine focus on the development of DPX extraction procedures for drugs of abuse in small volumes of urine, whole blood, and oral fluid. Chapter six involves the development of a single manual extraction method which can be used for both comprehensive and targeted drug screens. Forensic case samples were obtained from a local forensic toxicology laboratory to determine the effectiveness of this method on samples that contained drugs and metabolites due to actual exposure. In the subsequent chapters, this extraction method was used as the basis of an automated extraction procedure. A wholly automated extraction and analysis procedure for a mix of basic drugs in whole blood is described in chapter seven. Chapter eight adds an automated derivatization step for the analysis of THC and metabolites. A combination of derivatization reagents was determined to provide the best results for all three analytes. In chapter nine, the failures of online derivatization are demonstrated during the analysis of commonly abused opiates, thus requiring a separate off-line derivatization procedure. Additionally, the derivatization procedure was optimized to prevent a mixture of derivatization products for opiates that undergo keto-enol tautomerizations.