Analysis of Organophosphorus-Based Nerve Agent Degradation Products by Gas Chromatography-Mass Spectrometry (GC-MS): Current Derivatization Reactions in the Analytical Chemist's Toolbox.

Carlos A Valdez,Roald N Leif

doi:10.3390/molecules26154631

Carlos A Valdez, Roald N Leif

Open Access

https://doi.org/10.3390/molecules26154631

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Abstract

The field of gas chromatography-mass spectrometry (GC-MS) in the analysis of chemical warfare agents (CWAs), specifically those involving the organophosphorus-based nerve agents (OPNAs), is a continually evolving and dynamic area of research. The ever-present interest in this field within analytical chemistry is driven by the constant threat posed by these lethal CWAs, highlighted by their use during the Tokyo subway attack in 1995, their deliberate use on civilians in Syria in 2013, and their use in the poisoning of Sergei and Yulia Skripal in Great Britain in 2018 and Alexei Navalny in 2020. These events coupled with their potential for mass destruction only serve to stress the importance of developing methods for their rapid and unambiguous detection. Although the direct detection of OPNAs is possible by GC-MS, in most instances, the analytical chemist must rely on the detection of the products arising from their degradation. To this end, derivatization reactions mainly in the form of silylations and alkylations employing a vast array of reagents have played a pivotal role in the efficient detection of these products that can be used retrospectively to identify the original OPNA.

Highlights

Gas Chromatography-Mass Spectrometry (GC-MS) has been a central analytical technique in the field of Chemical Warfare Agent (CWA) detection, analysis, and identification.The role that this form of mass spectrometric method has provided to analysts immersed in this specific area is invaluable and continues to grow in importance as the chemical warfare agents (CWAs) molecular space rapidly expands
Interest in the field of derivatizations during the analysis of organophosphorus-based nerve agents (OPNAs) degradation products and those arising from chemical warfare agent (CWA) in general is always strengthened yearly during proficiency tests (PTs) administered by the Organisation for the Prohibition of Chemical Weapons (OPCW)
Within the field of GC-MS derivatization reactions continue to appear that provide invaluable assistance to the analytical chemist in the analysis of phosphonic acids and polar compounds related to OPNAs

Summary

Introduction

Gas Chromatography-Mass Spectrometry (GC-MS) has been a central analytical technique in the field of Chemical Warfare Agent (CWA) detection, analysis, and identification. The OPNA Tabun (or GA) is considered a G-series agent even though it does not share moiety. The OPNA Tabun (or GA) is considered a G-series agent even though it does many common features with the other the group. Of a methyl group.category, The second the consists of a pentavalent phosphorus atom featuring an alkoxy and a methyl substituent. V-series consists of a pentavalent phosphorus atom featuring an alkoxy and a methyl in addition in to addition a N,N-dialkylaminoethylthiolate group that serves a leaving group in its substituent to a N, N-dialkylaminoethylthiolate group as that serves as a leaving reaction with. For CVX, alkoxy group is the n-butoxy group while thioalkyl side chain substituent. CVX, the alkoxy group is the n-butoxy groupthe while the thioalkyl sideis the N,N-diethylaminoethylthiol substituent. OPNA synthesized [11,12,13]

Degradation

GC-MS as an Important Technique in the Analysis of Nerve Agent

Silylation of GC-MS analysis

Methylation Methods

Derivatization

Outlook and Concluding Remarks