Determination of diphenylamine stabilizer and its nitrated derivatives in smokeless gunpowder using a tandem MS method

Abstract

A novel method for determination of diphenylamine (DPA) and its nitrated derivatives, which are considered as characteristic components in smokeless powder and gunshot residues, is described. A tandem mass spectrometric method is established and mass spectrometer parameters optimized for each compound to obtain higher sensitivity. Under optimum conditions, quantitative analysis was carried out. The linear ranges are 5.0-200.0, 2.0-200.0 and 5.0-250.0 ng ml-1 and the detection limits are 1.0, 0.5 and 2.5 ng ml-1 for diphenylamine (DPA), N-NO-diphenylamine (N-NO-DPA) and 4-NO2-diphenylamine (4-NO2-DPA), respectively. Intra-assay and inter-assay precision and accuracy of analysis of these three samples were investigated. Based on the regression lines obtained above, smokeless samples were analyzed. It was found that there are 0.952% DPA, 0.384% N-NO-DPA and 0.128% 4-NO2-DPA in smokeless powder. Recovery tests showed that using cotton swabs, 80.3 +/- 4.9% DPA, 79.6 +/- 3.1% N-NO-DPA and 83.1 +/- 5.4% 4-NO2-DPA could be recovered from human hands.

Mobile phase influence on electrospray ionization for the analysis of smokeless powders by gradient reversed phase high-performance liquid chromatography-ESIMS

“…Initial studies on the analysis of smokeless powder components by HPLC-ESIMS and ESIMS/MS in the positive ion mode illustrated the detection of certain compounds but did not report the use of electrolytes to promote ionization [8,9,29]. Other investigations reporting the use of HPLC-ESIMS for smokeless powder analysis, including negative ion ESIMS studies, utilized ammonium acetate at arbitrarily chosen concentrations [2,8,11,29].…”

“…The use of electrospray ionization mass spectrometry (ESIMS) is becoming an important technique in forensic applications involving the analysis of toxicological and explosive samples [1][2][3][4][5][6][7][8][9][10][11][12]. The selection of the optimal ESIMS detection parameters involves consideration of analyte characteristics, instrument operation, and in regard to reversed phase high-performance liquid chromatography (HPLC), the mobile phase composition [10,[13][14][15][16].…”

Characterization of gunpowder samples using time-of-flight secondary ion mass spectrometry (TOF-SIMS)

“…In particular, it has become of great interest to differentiate between various gunpowder samples via determination of their additive composition. There are many technologies that can be used to determine the compositions of gunpowder samples including capillary electrophoresis (CE), energy dispersive X-ray spectroscopy (EDX), X-ray fluorescence (XRF), Raman microscopy, gas chromatography-mass spectrometry (GC/MS) (as well as many other mass spectrometry techniques), ion mobility spectrometry (IMS) and infrared analysis [1][2][3][4][5][6][7][8][9][10]. Due to its surface sensitivity, low detection limits, and imaging capabilities, time-of-flight secondary ion mass spectrometry (TOF-SIMS) is an ideal technique to use for analysis of gunpowder residues [11][12][13].…”

Synthesis and Characterization of Conjugated Pyridine-(N-diphenylamino) Acrylonitrile Derivatives: Photophysical Properties

“…et al, 2002). In addition, aromatic amines have been tested as blue emitters in organic LEDs (Tong, et al, 2004) and as components of electroluminescent bipolar devices (Justin Thomas, et al, 2002), while arylamines have been used in applications such as antioxidants (Tong, et al, 2001;Esteves, et al, 2001). Triphenylamines, with their characteristic propeller starburst molecular structure, have been widely used in opto-and electroactive materials due to their good electro-donating and transporting capabilities (Ning & Tian, 2009;Chen, et al, 2009;Zhang, et al, 2009).…”