Structural elucidation of V-type nerve agents by liquid chromatography/electrospray ionization mass spectrometry.
LC-ESI-MS/MS
N-iodosuccinimide
V-nerve agents
phosphonic acid hydrolysis products
structural elucidation
Journal
Journal of mass spectrometry : JMS
ISSN: 1096-9888
Titre abrégé: J Mass Spectrom
Pays: England
ID NLM: 9504818
Informations de publication
Date de publication:
Oct 2020
Oct 2020
Historique:
received:
01
06
2020
revised:
06
07
2020
accepted:
07
07
2020
entrez:
29
7
2020
pubmed:
29
7
2020
medline:
29
7
2020
Statut:
ppublish
Résumé
V-nerve agents present information-poor spectra, both in GC-EI-MS and LC-ESI-MS/MS, with dominant fragments/product ions corresponding to the amine-containing residue. Hence, derivatives/isomers with the same amine residue exhibit similar mass spectral patterns, leading to ambiguity in the phosphonate structure. We present a simple approach for their structural elucidation based on two complementary experiments: ESI-MS/MS of the original compound, which provides information about the amine moiety, and ESI-MS/MS of the phosphonic acid hydrolysis products generated by N-iodosuccinimide, which provides ions' characteristic of the phosphonate structure. This approach enables the structural elucidation of the original V-agents with a higher degree of certainty.
Types de publication
Journal Article
Langues
eng
Sous-ensembles de citation
IM
Pagination
e4617Informations de copyright
© 2020 John Wiley & Sons, Ltd.
Références
Convention on the Prohibition of the Development, Production, Stockpiling and Use of Chemical Weapons and on Their DestructionTechnical Secretariat of the Organisation for the Prohibition of Chemical Weapons, The Hague (1997) http://www.opcw.org
Snyder DT, Demond PS, Szalwinski LJ, et al. Two-dimensional MS/MS scans on a linear ion trap mass analyzer: identification of V-series chemical warfare agents. Int J Mass Spectrom. 2019;444:116171.
Smithson AE, Levy LA. Chapter 3-rethinking the lessons of Tokyo. Ataxia: The Chemical and Biological Terrorism Threat and the US Response (Report) 35. Washington, DC: Henry L. Stimson Centre; 1999.
Nakagawa T, Tu AT. Murders with VX: aum Shinrikyo in Japan and the assassination of Kim Jong-Nam in Malaysia. Forensic Toxicol. 2018;36(2):542-544.
Weissberg A, Madmon M, Dagan S. Derivatization and modification of chemical warfare agents and their related compounds for LC-MS-based analytical applications. Encyclopedia Anal Chem. https://onlinelibrary.wiley.com/doi/book/10.1002/9780470027318
Bell AJ, Murrell J, Timperley CM, Watts P. Fragmentation and reactions of two isomeric O-alkyl S-(2-dialkylamino)ethyl methylphosphonothiolates studied by electrospray ionization/ion trap mass spectrometry. J Am Soc Mass Spectrom. 2001;12(8):902-910.
Ellis-Steinborner S, Ramachandran A, Blanksby SJ. The fragmentation pathways of protonated Amiton in the gas phase: towards the structural characterisation of organophosphorus chemical warfare agents by electrospray ionisation tandem mass spectrometry. Rapid Commun Mass Spectrom. 2006;20(12):1939-1948.
Weissberg A, Tzanani N, Dagan S. Specificity enhancement by electrospray ionization multistage mass spectrometry-a valuable tool for differentiation and identification of ‘V’-type chemical warfare agents. J Mass Spectrom. 2013;48(12):1340-1348.
Housman KJ, Swift AT, Oyler JM. Fragmentation pathways and structural characterization of 14 nerve agent compounds by electrospray ionization tandem mass spectrometry. J Anal Toxicol. 2015;39(2):96-105.
Saeidian H, Mirkhani V, Faraz SM, Babri M. Unambiguous mass spectral characterization of VX and its six other structural isomers using gas chromatography-mass spectrometry. Int J Mass Spectrom. 2016;396:5-12.
Fukuto TR, Stafford EM. The isomerization of O,O-diethyl O-2-diethylaminoethyl phosphorothionate. J Am Chem Soc. 1957;79(22):6083-6085.
Smolkin B, Levi N, Karton-Lifshin N, Yehezkel L, Zafrani Y, Columbus I. Oxidative detoxification of sulfur-containing chemical warfare agents by electrophilic iodine. J Org Chem. 2018;83(22):13949-13955.
Kingery AF, Allen HE. The environmental fate of organophosphorus nerve agents: a review. Toxicol Environ Chem. 1995;47(3-4):155-184.
Black RM, Clark RJ, Read RW, Reid MTJ. In Proceedings of the ERDEC Scientific Conference on Chemical Defense Research, Aberdeen Proving Ground, MD, 1994, ERDEC-SP-024.
Wagner GW, MacIver BK. Degradation and fate of mustard in soil as determined by13C MAS NMR. Langmuir. 1998;14(24):6930-6934.
Mizrahi DM, Columbus I. 31P MAS NMR: a useful tool for the evaluation of VX natural weathering in various urban matrixes. Environ Sci Technol. 2005;39(22):8931-8935.
Columbus I, Waysbort D, Marcovitch I, Yehezkel L, Mizrahi DM. VX fate on common matrices: evaporation versus degradation. Environ Sci Technol. 2012;46(7):3921-3927.
Mizrahi DM, Goldvaser M, Columbus I. Long-term evaluation of the fate of sulfur mustard on dry and humid soils, asphalt, and concrete. Environ Sci Technol. 2011;45(8):3466-3472.
Fernández SF, Pastor A, Yusà V, Montesinos L, Pardo O. Development of a novel methodology for determination of dialkyl phosphates in human urine using liquid chromatography-tandem mass spectrometry. J Chromatogr B. 2019;1130-1131:121810.
Lagarrigue M, Bossée A, Bégos A, Varenne A, Gareil P, Bellier B. Separation and identification of isomeric acidic degradation products of organophosphorus chemical warfare agents by capillary electrophoresis-ion trap mass spectrometry. J Chromatogr A. 2006;1137(1):110-118.
Weissberg A, Dagan S. Interpretation of ESI(+)-MS-MS spectra-towards the identification of “unknowns”. Int J Mass Spectrom. 2011;299(2-3):158-168.