Development of a method for the derivatization of ethanolamines and its application to sand samples

Rozsypal, Tomas

doi:10.2298/jsc210312047r

Cited by 9 publications

(7 citation statements)

References 20 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…For procedures in mobile laboratories, extraction by ultrasonication from various types of matrices is often recommended, 29 which represents a relatively undemanding method of extraction, but on the other hand, the sample is heated during the procedure. As we have demonstrated in the past, in the case of sand, mechanical vortex shaking is more suitable 31,32 . The results of the various procedures that were tested are presented in Table 4.…”

Section: Resultsmentioning

confidence: 91%

See 1 more Smart Citation

Contaminated disposable rubber gloves as evidence samples after a chemical attack with nerve agents

Rozsypal

2023

Drug Testing and Analysis

Self Cite

View full text Add to dashboard Cite

Nerve agents have been used recently in the Syrian civil war. Collecting relevant samples for retrospective identification of an attack is often problematic. The article deals with the possibility of using contaminated gloves as an analytical sample for evidence of the chemical weapons use. There have not yet been published studies dealing with the identification of chemical warfare agents in this type of matrix, where the diversity of chemical properties of gloves and the lifetime of the contaminated sample would be considered. Sarin, soman, and cyclosarin were used as contaminants in the study. Nitrile, latex, and vinyl disposable gloves were chosen as matrices. The identification method was gas chromatography. Six solvents commonly used in military laboratories were tested as extractants. The extraction procedure was optimized in terms of the appropriate method (vortex) and the required extraction time (1 min) and resulted in significant reduction in sample preparation time. The chromatographic background of the extracts was also monitored in order to find a method with the least number of peaks interfering in the identification. Suitable solvents were hexane and acetonitrile. The lifetime of the sample was also investigated. The worst result was recorded for latex. For individual contaminants, the time varied depending on the volatility. The developed procedures were successfully validated within a sample handling effects scenario. The results demonstrate that in the event of an ongoing military risk at the site of an attack, even discarded disposable rubber glove type samples can be used as evidence.

show abstract

Section: Resultsmentioning

confidence: 91%

“…As we have demonstrated in the past, in the case of sand, mechanical vortex shaking is more suitable. 31,32 The results of the various procedures that were tested are presented in Table 4. The model substance was GF.…”

Section: Selection Of An Optimal Methods Of Analyte Extraction From R...mentioning

confidence: 99%

Contaminated disposable rubber gloves as evidence samples after a chemical attack with nerve agents

Rozsypal

2023

Drug Testing and Analysis

Self Cite

View full text Add to dashboard Cite

show abstract

“…soil and asphalt) is extraction with an organic solvent. The extraction efficiencies of NMs from soil utilizing various organic solvents are above 50% 16 . However, many organic solvents are not compatible with LC/MS analysis.…”

Section: Resultsmentioning

confidence: 99%

“…The extraction efficiencies of NMs from soil utilizing various organic solvents are above 50%. 16 However, many organic solvents are not compatible with LC/MS analysis. As our study focused on the development of an LC/MS/MS-based method for the detection of NMs, ethanol was selected as a compatible solvent for LC/MS analysis, in addition to its extraction capability, which was probably good.…”

Section: Optimization Of Conditions For Ethanolysis Of Nmsmentioning

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

View full text Add to dashboard Cite

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.

show abstract

“…To partially circumvent this issue, a variety of derivatization methods aimed at the conversion of these polar compounds into species possessing superior GC profiles than those of the starting materials have been devised. Specifically, for ethanolamines, some of these methods have involved silylation using BSTFA [14,15], MTBSTFA [16], or the NMI-mediated activation protocol [17,22], as well as equally efficient fluorinations in the form of trifluoroacetyl and heptafluorobutyryl tags [23][24][25]. Even though silylation and acylation are efficient at providing derivatives for N,N-disubstituted ethanolamines, these derivatives are prone to hydrolysis under slightly basic conditions (pH ~ 8-9) unless the amount of steric hindrance on these tags is greatly increased [26].…”

Section: Re Sults and Discussionmentioning

confidence: 99%

Practical benzylation of N,N‐substituted ethanolamines related to chemical warfare agents for analysis and detection by electron ionization gas chromatography–mass spectrometry

Valdez

Hok

et al. 2023

Journal of Forensic Sciences

View full text Add to dashboard Cite

The benzylation of three low molecular weight N,N‐disubstituted ethanolamines related to chemical warfare agents (CWAs) to furnish derivatives with improved gas chromatography‐mass spectrometry (GC‐MS) profiles is described. Due to their low molecular weight and polar nature, N,N‐disubstituted ethanolamines are notoriously difficult to detect by routine GC‐MS analyses during Organisation for the Prohibition of Chemical Weapons (OPCW) proficiency tests (PTs), particularly in scenarios when they are present at low levels (~1–10 ppm) amidst more abundant interferences. Our studies revealed that the optimal derivatization conditions involved the treatment of the ethanolamine with benzyl bromide in the presence of an inorganic base (e.g., Na2CO3) in dichloromethane at 55°C for 2 h. This optimized set of conditions was then successfully applied to the derivatization of N,N‐dimethylethanolamine, N,N‐diethylethanolamine and N,N‐diisopropylethanolamine present separately at 1 and 10 μg/mL concentrations in a glycerol‐rich matrix sample featured in the 48th OPCW PT. The benzylated derivatives of the three ethanolamines possessed retention times long enough to clear the massive glycerol‐containing matrix interferences. The protocol herein is introduced as an alternative method for derivatization of these CWA and pharmaceutically important species and should find broad applicability in laboratories where routine forensic analysis is carried out.

show abstract

Development of a method for the derivatization of ethanolamines and its application to sand samples

Cited by 9 publications

References 20 publications

Contaminated disposable rubber gloves as evidence samples after a chemical attack with nerve agents

Contaminated disposable rubber gloves as evidence samples after a chemical attack with nerve agents

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

Practical benzylation of N,N‐substituted ethanolamines related to chemical warfare agents for analysis and detection by electron ionization gas chromatography–mass spectrometry

Contact Info

Product

Resources

About