Study On The Applications Of Liquid Chromatography-Linear Ion Trap Mass Spectrometry Coupled With On-Line Solid Phase Extraction In Analysis Of Several Types Of Forensic Toxicants

As common detection objects of forensic toxicology analysis, biological samples such as urine and blood are characterized by the complex matrix, limited amount of samples, and low concentration of analytes. For these reasons, efficient pre-treatment methods and sensitive detection techniques are both required for analysis of biological samples. In this thesis, bioanalytical methods for several types of forensic toxicants were established by using liquid chromatography-linear ion trap mass spectrometry (LC-LIT/MS) with the application of on-line solid phase extraction (SPE) technology, which realized the automated and efficient treatment of samples. These analysis methods have an important guiding significance to the work of physical and chemical inspection for public security departments.(1) A quantitative method was established for the analysis of seven anticoagulant rodenticides in whole blood and urine samples by on-line SPE/LC-LIT/MS. Automated on-line treatment and analysis were carried out after simple pre-treatment of the samples. Satisfactory peak shape and separation were obtained by optimization of the on-line SPE and chromatographic conditions. MS2 full-scan data of parent ions within the given time window was recorded for qualitative analysis. Highly sensitive MS2 daughter ions were selected for quantitative analysis. Finally, low detection limits of 0.02-1.00 ng/mL were obtained in this analytical method.(2) A sensitive method was established for the analysis of eighteen carbamate pesticides in whole blood, urine, and liver tissue samples by on-line SPE/LC-LIT/MS. Automated on-line treatment and analysis were carried out after simple pre-treatment of the samples. Analytical conditions, such as the mobile phase, tube lens, and factors associated with on-line SPE, were fully optimized. Selected reaction monitoring (SRM) scan mode was used for MS detection of six pesticides. Consecutive reaction monitoring (CRM) scan mode was used for the other twelve, which was reported for the first time. The optimized method showed high sensitivity and selectivity, with detection limits of 0.1-5.0 ng/mL in whole blood and urine,0.1-5.0 ng/g in liver tissue, respectively.(3) A rapid quantitative method was established for the analysis of seven aconitum alkaloids in whole blood, urine, and liver tissue samples by on-line SPE/LC-LIT/MS. MS fragmentation regularities of the analytes were studied and summarized. Automated on-line treatment and analysis were carried out after simple pre-treatment of the samples. The on-line SPE and chromatographic conditions were fully optimized. With strong specificity, CRM scan mode was used for MS analysis. Detection limits obtained by the established method were very low, with 0.02-0.60 ng/mL in whole blood and urine,0.02-0.40 ng/g in liver tissue, respectively.(4) An accurate method was established for the analysis of sixteen opioids and metabolites in whole blood, urine, and liver tissue samples by on-line SPE/LC-LIT/MS. Automated on-line treatment and analysis were carried out after enzymatic hydrolysis and simple pre-treatment of the samples. After optimization of the hydrolysis time, on-line SPE, and chromatographic conditions, satisfactory separation was achieved for the sixteen analytes with similar polarity. CRM scan mode was used for MS analysis, which was reported for the first time. Optimization of the qualitative and quantitative ion pairs was performed. The method established was proved to be sensitive and accurate.