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- Title
Mass spectral studies of silyl derivatives of partially hydrolyzed products of nitrogen mustards: Important markers of nitrogen mustard exposure.
- Authors
Chandra, Buddhadeb; Sinha Roy, Kanchan; Shaik, Mahabul; Waghmare, Chandrakant; Palit, Meehir
- Abstract
Rationale: Nitrogen mustards (NMs) are vesicant class of chemical warfare agents. From the viewpoint of the Chemical Weapons Convention partially hydrolyzed products of nitrogen mustards (pHpNMs) are considered as important markers of nitrogen mustard exposure. The detection of pHpNMs from biological or environmental samples is highly useful for obtaining forensic evidence of exposure to NMs. Methods: Gas chromatography interfaced with tandem mass spectrometry (GC/MS/MS) is a widely used tool for the identification and sensitive detection of metabolites of NMs in complex matrices. The pHpNMs were derivatized using silylating agents as they are highly polar and non‐amenable to GC. The mass spectral studies of these silyl derivatives of pHpNMs were performed using GC/MS/MS in both electron ionization (EI) and chemical ionization (CI) mode. Results: Various approaches have been proposed to assess the fragmentation pathways of the trimethylsilyl (TMS) and tert‐butyldimethylsilyl (TBDMS) derivatives of pHpNMs. All the proposed fragmentation pathways were based on the product and/or precursor ion scanning of corresponding ions in both EI and CI mode. In the case of EI, most of the fragmentation pathways involved either α‐cleavage or inductive cleavage. Conclusions: This is the first report on the MS study of the silyl derivatives of pHpNMs. The study of the two different derivatives of pHpNMs using both EI‐ and CI‐MS provides a reliable, unambiguous identification of pHpNMs in complex environmental and biomedical matrices (such as plasma and urine) during any verification activities.
- Subjects
NITROGEN mustards; CHEMICAL warfare agents; TANDEM mass spectrometry; ELECTRON impact ionization; ENVIRONMENTAL forensics; COMPLEX matrices; FRAGMENTATION reactions; METABOLITES
- Publication
Rapid Communications in Mass Spectrometry: RCM, 2020, Vol 34, Issue 3, pN.PAG
- ISSN
0951-4198
- Publication type
Article
- DOI
10.1002/rcm.8586