Premium
Mass spectral studies of silyl derivatives of partially hydrolyzed products of nitrogen mustards: Important markers of nitrogen mustard exposure
Author(s) -
Chandra Buddhadeb,
Sinha Roy Kanchan,
Shaik Mahabul,
Waghmare Chandrakant,
Palit Meehir
Publication year - 2020
Publication title -
rapid communications in mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.528
H-Index - 136
eISSN - 1097-0231
pISSN - 0951-4198
DOI - 10.1002/rcm.8586
Subject(s) - chemistry , silylation , fragmentation (computing) , electron ionization , mass spectrometry , trimethylsilyl , nitrogen , bstfa , chromatography , hydrolysis , tandem mass spectrometry , gas chromatography , gas chromatography–mass spectrometry , organic chemistry , ionization , ion , computer science , catalysis , operating system
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.