A novel approach for the detection and identification of sulfur mustard using liquid chromatography–electrospray ionization–tandem mass spectrometry based on its selective oxidation to sulfur mustard monoxide with <i>N</i>‐iodosuccinimide

Prihed, Hagit; Shifrovich, Avital; Yamin, Tamar Shamai; Madmon, Moran; Smolkin, Boris; Chen, Ravit; Blanca, Merav; Weissberg, Avi

doi:10.1002/jms.4721

Cited by 7 publications

(4 citation statements)

References 35 publications

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“…Recently, we reported a methodology for the sensitive determination of the intact SM blistering agent in the environment by oxidation with N-iodosuccinimide 29 or by a nucleophilic substitution reaction with diethanolamine, 30 followed by LC-electrospray ionization (ESI)-MS/MS analysis. We were further motivated to develop a method utilizing chemical derivatization for the sensitive detection and unambiguous identification of NMs in real-world environmental matrices, which is of prime importance from a forensic and verification viewpoint of the CWC.…”

Section: Introductionmentioning

confidence: 99%

Ethanolysis of nitrogen mustards: A novel strategy for nitrogen mustard identification in environmental matrices by liquid chromatography–electrospray ionization–tandem mass spectrometry

Belay,

Shifrovitch,

Prihed

et al. 2024

Rapid Comm Mass Spectrometry

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RationaleNitrogen mustards (NMs) are blistering chemical warfare agents. The ability to detect NMs in environmental samples is very important for obtaining forensic evidence. The most common analytical techniques for NM detection are gas chromatography–mass spectrometry, which detects NMs in their intact form but is disadvantaged by high limits of detection (LODs), and liquid chromatography–electrospray ionization–tandem mass spectrometry (LC/ESI‐MS/MS) of their hydrolysis products, which do not provide robust evidence to support NM use.MethodsWe developed a novel approach to detect and identify NMs using LC/ESI‐MS/MS after chemical derivatization. The method is based on ethoxide‐promoted ethanolysis prior to analysis. The effects of reaction time, temperature, ethoxide concentration and chromatography behavior were studied and optimized. In the developed procedure, 0.1% (v/v) sodium ethoxide solution is added to the NMs in ethanol and agitated for 2 h at 50°C, followed by LC/ESI‐MS/MS, without any other pretreatment.ResultsThe ethanolysis reaction efficiencies were evaluated in ethanolic extracts from soil, asphalt, and ethanol contaminated with 0.5% (v/v) diesel fortified with NMs at a five‐point calibration curve. The calibration curves showed good linearity in the range of 0.05–1 ng/mL, with an R2 value of 0.99, and were similar to those of LC/MS‐grade ethanol, with almost no observable matrix effects. The derivatization products were stable at room temperature, with LODs of 10 pg/mL, in all investigated extracts.ConclusionsThrough this newly developed strategy, the derivatization of active NMs by ethanolysis was achieved for the first time, and these derivatization products can serve as specific indicators for the use and presence of NMs. The methodology can also verify trace levels of NM chemical warfare agents collected in war or terror scenarios in forensic investigations.

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Section: Introductionmentioning

confidence: 99%

Ethanolysis of nitrogen mustards: A novel strategy for nitrogen mustard identification in environmental matrices by liquid chromatography–electrospray ionization–tandem mass spectrometry

Belay,

Shifrovitch,

Prihed

et al. 2024

Rapid Comm Mass Spectrometry

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“…Ethanol amines (EAs) are recognized as the markers for the detection of NMs in the environment and biological samples (seen in Figure 1 ); they are generated by the replacement of chlorine atoms by hydroxy groups [ 7 , 8 ]. In contrast to SMs, for which numerous analytical methods had been established [ 9 , 10 , 11 ], few detection technologies for NMs have been employed. Liquid chromatography-mass spectrometry (LC-MS) or gas chromatography-mass spectrometry (GC-MS) techniques have been utilized for the detection of EAs [ 7 , 12 , 13 ].…”

Section: Introductionmentioning

confidence: 99%

Highly Efficient Separation of Ethanol Amines and Cyanides via Ionic Magnetic Mesoporous Nanomaterials

Zhao,

Yang,

et al. 2024

IJMS

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Simple and efficient sample pretreatment methods are important for analysis and detection of chemical warfare agents (CWAs) in environmental and biological samples. Despite many commercial materials or reagents that have been already applied in sample preparation, such as SPE columns, few materials with specificity have been utilized for purification or enrichment. In this study, ionic magnetic mesoporous nanomaterials such as poly(4-VB)@M-MSNs (magnetic mesoporous silicon nanoparticles modified by 4-vinyl benzene sulfonic acid) and Co2+@M-MSNs (magnetic mesoporous silicon nanoparticles modified by cobalt ions) with high absorptivity for ethanol amines (EAs, nitrogen mustard degradation products) and cyanide were successfully synthesized. The special nanomaterials were obtained by modification of magnetic mesoporous particles prepared based on co-precipitation using -SO3H and Co2+. The materials were fully characterized in terms of their composition and structure. The results indicated that poly(4-VB)@M-MSNs or Co2+@M-MSNs had an unambiguous core-shell structure with a BET of 341.7 m2·g−1 and a saturation magnetization intensity of 60.66 emu·g−1 which indicated the good thermal stability. Poly(4-VB)@M-MSNs showed selective adsorption for EAs while the Co2+@M-MSNs were for cyanide, respectively. The adsorption capacity quickly reached the adsorption equilibrium within the 90 s. The saturated adsorption amounts were MDEA = 35.83 mg·g−1, EDEA = 35.00 mg·g−1, TEA = 17.90 mg·g−1 and CN−= 31.48 mg·g−1, respectively. Meanwhile, the adsorption capacities could be maintained at 50–70% after three adsorption–desorption cycles. The adsorption isotherms were confirmed as the Langmuir equation and the Freundlich equation, respectively, and the adsorption mechanism was determined by DFT calculation. The adsorbents were applied for enrichment of targets in actual samples, which showed great potential for the verification of chemical weapons and the destruction of toxic chemicals.

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“…All this justifies the investment of resources and the development of research programs aiming at the detection and/or the chemical neutralization of CWAs. [14][15][16][17][18][21][22][23][24][25][26][27][28] Mustard gas (HD, 1-chloro-2-[(2-chloroethyl)sulfanyl] ethane, CAS 505-60-2, Fig. 1) is a viscous liquid with vesicant (blistering) properties that causes severe damage to the eyes, skin, and respiratory tract.…”

Section: Introductionmentioning

confidence: 99%

A continuous flow generator of organic hypochlorites for the neutralization of chemical warfare agent simulants

et al. 2022

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A novel approach for the detection and identification of sulfur mustard using liquid chromatography–electrospray ionization–tandem mass spectrometry based on its selective oxidation to sulfur mustard monoxide with N‐iodosuccinimide

Cited by 7 publications

References 35 publications

Ethanolysis of nitrogen mustards: A novel strategy for nitrogen mustard identification in environmental matrices by liquid chromatography–electrospray ionization–tandem mass spectrometry

Ethanolysis of nitrogen mustards: A novel strategy for nitrogen mustard identification in environmental matrices by liquid chromatography–electrospray ionization–tandem mass spectrometry

Highly Efficient Separation of Ethanol Amines and Cyanides via Ionic Magnetic Mesoporous Nanomaterials

A continuous flow generator of organic hypochlorites for the neutralization of chemical warfare agent simulants

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