以即時直接分析離子源串聯式四極柱軌道式離子阱高解析質譜儀快速偵測微量有機顏料及非法藥物在刑事鑑定之應用

Abstract

一、 以即時直接分析離子源串聯式四極柱軌道式離子阱質譜儀分析微量液態非法藥物 即時直接分析離子源串聯式四極柱軌道式離子阱高解析質譜(DART- MS)無需要複雜之前處理過程，可直接分析常見以及新興的微量非法藥物。液態毒品通常毒品含量非常少，常見非法藥物為甲基安非他命(Methamphetamine) 、愷他命 (Ketamine) 、硝甲西泮 (Nimetazepam)等，近期發現新興非法藥物有對甲基乙基卡西酮 (p-Methethcathitone; 4-MEC)、對氯安非他命 (p-Chloroamphetamine; PCA)、4-氟甲基安非他命(p -Fluoromethamphetamine; 4-FMA)，3,4-亞甲基雙氧焦二異丁基酮(3,4-Methylenedioxypyrovalerone; MDPV)、3,4-亞甲基雙氧甲基卡西酮（Methylone; bk-MDMA）等成分，含量通常在數百個到數千個PPM之間。以DART (Direct Analysis in Real Time ) 作為離子源，可快速轉換離子為正負電荷，無須前處理，可得到毒品化合物帶正電荷質子或負電荷去質子之分子量。另可透過二次質譜 (product ion mass) 確認化合物，分析時間約數十秒，可快速篩檢且所需樣品量少，無須進行萃取及衍生化等前處理，樽節剩餘樣品可用以其他分析。 二、 以即時分析離子源串聯式四極柱軌道式離子阱質譜儀分析微量有機顏料 車漆鑑識在交通事故中，扮演著重要關鍵角色，例如肇事逃逸案件。而有機顏料比例通常在車漆成分中約1%左右，甚至更低，在車漆成分中分析不易。以即時直接分析離子源串聯式四極柱軌道式離子阱高解析質譜(DART-MS)直接分析車漆中之有機顏料，本研究共分析紅色、黃色、橘色以及紫色等計12種常見有機顏料，並針對個別有機顏料PR254，PV23以及PV19等顏料與樹脂進行塗裝後，分析該紅色及紫色有機顏料，成功得到該有機顏料一次及二次質譜訊號並建立資料庫。另外針對2個案件實例，也可準確分析微量轉移漆中包含之有機顏料，無須複雜的前處理，且分析時間少於1分鐘，相較於其他方法，可快速分析車漆中之有機顏料，增加交通事故中油漆成分的比鑑數據。

1. Using DART-coupled Q-orbitrap Tandem Mass Spectrometry for Rapid in Detection of Multiple Illicit Liquid Street Drugs Direct analysis in real time coupled to Q-orbitrap tandem mass Spectrometry (DART- MS) without requiring preparatory procedures was used to directly detect trace amounts of illegal street drugs, namely p-chloroamphetamine, p-fluoromethamphetamine, -hydroxybutyrate, ketamine, methamphetamine, 3,4-methylenedioxypyrovalerone, p-methylethcathinone, methylone, and nimetazepam, in solution and also in real drug samples. Exact mass determination of the drug samples was completed in less than 1 min. With the ability to rapidly identify drugs, this technique shows great potential as a useful analytical tool in the analysis of illicit street drugs, and has the significant advantages of simplicity and sensitivity without the sample preparation needed by other methods.

2. Direct Identification of Organic Pigment in Car Paints by DART-Coupled Q-orbitrap Tandem Mass Spectrometry The appropriate examination of paint fragments involved in an accident, such as a hit-and-run case, is often critical in forensic studies. However, organic pigments are usually minor components of automotive coatings; thus, it is difficult to discriminate them. This thesis demonstrates the utility of direct analysis in real time mass spectrometry (DART-MS) for the detection of a wide range of common organic pigments in vehicle paint. Twelve common organic pigments used in vehicle paints including red, yellow, orange, and purple were tested to provide a database for future vehicle paint examination. Two hit-and-run vehicle accidents cases happened in New Taipei City have been investigated with Fourier transform infrared spectroscopy (FTIR) and direct analysis in real time mass spectrometry (DART-MS). FTIR spectroscopy was first used to study the paint samples as a preliminary screening step. Most IR peaks come from binder and extenders. IR peaks of organic pigments were found to be weak and overlapped by resins. In contrast, the complete chemical characterization of organic pigments could be easily identified using DART-MS. DART-MS provides an excellent means to rapidly determine the presence of organic pigments in paint samples without a complicated pre-treatment or lengthy analysis time.