Tomlinson-Phillips Jill, Wooten Alfred, Kozole Joseph, Deline James, Beresford Pamela, Stairs Jason
ORISE Fellow at the U.S. Department of Homeland Security, Science & Technology Directorate, Transportation Security Laboratory, USA.
Battelle Memorial Institute, 2900 Fire Rd, Suite 201, Egg Harbor Township, NJ 08234, USA.
Talanta. 2014 Sep;127:152-62. doi: 10.1016/j.talanta.2014.03.044. Epub 2014 Apr 2.
Identification of the fragment ion species associated with the ion reaction mechanism of triacetone triperoxide (TATP), a homemade peroxide-based explosive, is presented. Ion mobility spectrometry (IMS) has proven to be a key analytical technique in the detection of trace explosive material. Unfortunately, IMS alone does not provide chemical identification of the ions detected; therefore, it is unknown what ion species are actually formed and separated by the IMS. In IMS, ions are primarily characterized by their drift time, which is dependent on the ion׳s mass and molecular cross-section; thus, IMS as a standalone technique does not provide structural signatures, which is in sharp contrast to the chemical and molecular information that is generally obtained from other customary analytical techniques, such as NMR, Raman and IR spectroscopy and mass spectrometry. To help study the ion chemistry that gives rise to the peaks observed in IMS, the hardware of two different commercial IMS instruments has been directly coupled to triple quadrupole (QQQ) mass spectrometers, in order to ascertain each ion׳s corresponding mass/charge (m/z) ratios with different dopants at two temperatures. Isotope labeling was then used to help identify and confirm the molecular identity of the explosive fragment and adduct ions of TATP. The m/z values and isotope labeling experiments were used to help propose probable molecular formulas for the ion fragments. In this report, the fragment and adduct ions m/z 58 and 240 of TATP have been confirmed to be C3H6NH·H and TATP·NH4, respectively; while the fragment ions m/z 73 and 89 of TATP are identified as having the molecular formulas C4H9NH2 and C4H9O2, respectively. It is anticipated that the work in this area will not only help to facilitate improvements in mobility-based detection (IMS and MS), but also aid in the development and optimization of MS-based detection algorithms for TATP.
本文介绍了与自制过氧化物基炸药三丙酮三过氧化物（TATP）离子反应机理相关的碎片离子种类的鉴定。离子迁移谱（IMS）已被证明是检测痕量爆炸物材料的关键分析技术。不幸的是，仅靠IMS无法对检测到的离子进行化学鉴定；因此，尚不清楚IMS实际形成并分离的是什么离子种类。在IMS中，离子主要通过其漂移时间来表征，漂移时间取决于离子的质量和分子横截面；因此，作为一种独立技术，IMS无法提供结构特征，这与通常从其他常规分析技术（如核磁共振、拉曼光谱、红外光谱和质谱）获得的化学和分子信息形成鲜明对比。为了帮助研究导致在IMS中观察到的峰的离子化学，两种不同商业IMS仪器的硬件已直接与三重四极杆（QQQ）质谱仪耦合，以便在两个温度下确定不同掺杂剂时每个离子相应的质荷比（m/z）。然后使用同位素标记来帮助鉴定和确认TATP的爆炸碎片和加合离子的分子身份。m/z值和同位素标记实验用于帮助提出离子碎片可能的分子式。在本报告中，已确认TATP的碎片离子和加合离子m/z 58和240分别为C3H6NH·H和TATP·NH4；而TATP的碎片离子m/z 73和89分别被鉴定为具有分子式C4H9NH2和C4H9O2。预计该领域的工作不仅将有助于促进基于迁移率的检测（IMS和MS）的改进，还将有助于开发和优化基于MS的TATP检测算法。
