Centro de Documentação da PJ
Monografia

2811019.D.95
BELCHIOR, Filipa
Accurate mass analyses of peroxides explosives / Filipa Belchior.- [Stoke on Trent] ; [Seven Oaks] : [s.n.], 2006.- vi, 136 f., anexos ; 30 cm
Degree of Masters of Science in Forensic Science, Faculty of Health and of Sciences (Staffordshire University) and Forensic Explosives Laboratory/Defense Science and Technology Laboratory.

ANÁLISE LABORATORIAL, ENGENHO EXPLOSIVO, QUÍMICA ANALÍTICA, CIÊNCIA FORENSE, TESE

1. Introduction. 1.1 Aim of the project. 1.2 Background. 1.3 The Forensic Explosives Laboratory (FEL). 1.4 Explosives. 1.4.1 Definition. 1.4.2 Classification. 1.5 Historical reported use of he peroxide explosives 3,3,6,6,9,9-hexamethyl 1,2,4,5,7,8-hexoxonane (TATP) and 3,4,8,9,12,13-hexaoxa-1,6 diazabicyclo[ 4,4,4] tetradecane (HMTD). 1.5.1 TATP. 1.5.1.1 Molecular structure and properties. 1.5.1.2 Preparation of TATP. 1.5.1.3 TATP decompositions reactions. 1.5.2 HMTD. 1.5.2.1 Molecular structure and properties. 1.5.2.2 Preparation. 1.5.2.3 HMTD decompositions reactions. 1.6 Forensic analysis of peroxides explosives. 1.6.1 Spot tests. 1.6.2 Thermal methods. 1.6.3 Enzymatic reactions. 1.6.4 Separation methods. 1.6.5 Spectroscopic techniques. 1.6.6 Spectrometric techniques. 1.6.6.1 Mass spectrometry. 1.6.7 Chromatographic techniques hyphenated with mass spectrometry. 1.7 Liquid chromatography with mass spectrometry and tandem mass spectrometry (LC/MS and LC/MS/MS). 1. 7.1 Liquid chromatographic systems. 1.7.2 LC/MS and LC/MS/MS ion sources. 1.7.3 Quadrupole analysers. 1.7.4 Tandem mass spectrometry. 1.8 Mass spectra of TATP and HMTD. 1.8.1 TATP spectra. 1.8.2 HMTD spectra. 1.9 Accurate mass. 1.9.1 Accurate mass measurements. 1.9.2 Amount of error. 1.9.3 Lock fiasses. 2. EXPERIMENTAL. 2.1 Apparatus and laboratory conditions. 2.2 Preparation of solutions. 2.3 to 2.12 Methods and analyses. 2.3 LC/MS/MS initial conditions. 2.4 Liquid chromatography instrumental conditions. 2.5 Robustness and repeatability of the injection modes; sensitivity. 2.6 Instrument calibration for accurate mass measurements. 2.7 Optimisation of TATP m/z values and instrument parameters. 2.8 Accurate mass analyses of TATP parent ions m/z 89 and m/z 240. 2.8.1 With PEG-200 ammoniated species as lock masses. 2.8.2 With PEG-200 protonated species as lock masses. 2.8.3 With PEG-200 ammoniated species and methanol clusters as lock masses. 2.8.4 With methanol clusters as lock masses. 2.9 Optimisation of the method and mobile phase for the analysis of HMTD. 2.9.1 Mobile phase methanol/water. 2.9.2 Mobile phase acetonitrile/water. 2.10 Determination of HMTD product ions. 2.11 HMTD tune parameters optimisation and background evaluation. 2.12 Accurate mass analyses of HMTD ions. 2.12.1 Accurate mass analyses of parent ions m/z 179, m/z 207 and m/z 209. 2.12.2 Accurate mass analyses of product ions. 3. Results and discussion. 3.1. Liquid chromatography instrumental conditions. 3.1.1 Carry over and peak shape. 3.1.2 Robustness and repeatability of injection modes; sensitivity. 3.2 TATP methods and accurate mass analyses. 3.2.1 Optimisation of parent ions m/z values and instrument parameters. 3.2.2 Accurate mass measurements of m/z 89 and m/z 240. 3.2.2.1 With PEG-200 ammoniated species as lock masses. 3.2.2.2 With PEG-200 protonated species as lock masses. 3.2.2.3 With PEG-200 ammoniated species and methanol clusters as lock masses. 3.2.2.4 Using methanol clusters as lock masses. 3.3 HMTD methods and accurate mass analyses. 3.3.1 Optimisation of the method and mobile phase for HMTD analyses. 3.3.2 Determination of HMTD productions. 3.3.3. Evaluation of the background with PEG solution. 3.3.4 Accurate mass results of HMTD parent ions. 3.3.4.1 Accurate mass measurement of the m/z. 3.3.4.2 Accurate mass measurement of the m/z 209. 3.3.4.3 Accurate mass measurement of the m/z 207 . 3.3.5 Accurate mass determinations of HMTD product ions. 3.3.5.1 Accurate mass measurement of product ions of m/z 179. 3.3.5.2 Accurate mass measurement of product ions of m/z 207. 3.3.5.3 Accurate mass measurement of product ions of m/z 209. 4. Conclusions. 4.1. LC/MS/MS instrumental conditions. 4.2 Accurate mass measurements. 4.3 TATP accurate mass results. 4.4 HMTD accurate mass results. 4.5 Accurate mass results in the forensic field. 5. Further work. 6. References. Appendices.