The identification of chemical attribution signatures of stored VX nerve agents using NMR, GC-MS, and LC-HRMS

Ovenden, Simon P. B.; Webster, Renée L.; Micich, Eva; McDowall, Lyndal; McGill, Nathan W; Williams, Jilliarne; Zanatta, Shannon D.

doi:10.1016/j.talanta.2020.120753

Cited by 20 publications

(19 citation statements)

References 26 publications

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“…[67][68][69][70][71][72][73] This emerging field, rapidly developing in analytical chemistry, has found significant application particularly in the forensic analysis of samples associated not only with fentanyls but other chemical warfare agents. [74][75][76][77][78] Throughout this review, great effort has been placed in providing a brief introduction of the synthetic methods used to construct the discussed fentanyls as well as clear schematics that describe these pathways.…”

Section: Fentanyl: the Flagship Synthetic Opioidmentioning

confidence: 99%

Gas Chromatography-Mass Spectrometry Analysis of Synthetic Opioids Belonging to the Fentanyl Class: A Review

Valdez

2021

Critical Reviews in Analytical Chemistry

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The rising number of deaths caused by fentanyl overdosing in the US due to the overwhelming illicit use of this synthetic opioid has started a global campaign to develop efficient ways to control its production and distribution as well as discovering efficient antidotes to mitigate its lethal effects. Another important vein of focused research established by various agencies lies in the development of efficient and practical protocols for the detection of this opioid and analogs thereof in various matrices, whether environmental or biological in nature, particularly in the field of gas chromatography-mass spectrometry (GC-MS). The following review will cover the literature dealing with the detection and identification of synthetic opioids belonging to the fentanyl class by GC-MS means and hyphenated versions of the technique. Detailed descriptions will be given for the GC-MS methods employed for the analysis of the opioid, starting with the nature of the extraction protocol employed prior to analysis to the actual findings presented by the cited reports. Great effort has gone into describing the methods involved in each paper in a detailed manner and these have been compiled by year in tables at the end of each section for the reader's convenience. Lastly, the review will end with concluding remarks about the state of GC-MS analysis with regards to these powerful opioids and what lies ahead for this analytical field.

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Section: Fentanyl: the Flagship Synthetic Opioidmentioning

confidence: 99%

Gas Chromatography-Mass Spectrometry Analysis of Synthetic Opioids Belonging to the Fentanyl Class: A Review

Valdez

2021

Critical Reviews in Analytical Chemistry

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“…Source attribution means to trace the agent back to a specific synthesis method, reaction batch, specific precursor chemicals, or an existing stockpile. The chemical signatures of environmental samples have been the subject of academic interest [ 51 – 54 ] but have also been used in real cases [ 55 ]. So far, biomedical samples have not been considered for source attribution for several reasons: The intact chemical agent and the potential by-products and impurities are normally no longer present in vivo.…”

Section: Resultsmentioning

confidence: 99%

Adduct of the blistering warfare agent sesquimustard with human serum albumin and its mass spectrometric identification for biomedical verification of exposure

Blum¹,

Richter

Siegert

et al. 2020

Anal Bioanal Chem

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Apart from the well-known sulfur mustard (SM), additional sulfur-containing blistering chemical warfare agents exist. Sesquimustard (Q) is one of them and five times more blistering than SM. It is a common impurity in mustard mixtures and regularly found in old munitions but can also be used in pure form. Compared to the extensive literature on SM, very little experimental data is available on Q and no protein biomarkers of exposure have been reported. We herein report for the first time the adduct of Q with the nucleophilic Cys34 residue of human serum albumin (HSA) formed in vitro and introduce two novel bioanalytical procedures for detection. After proteolysis of this HSA adduct catalyzed either by pronase or by proteinase K, two biomarkers were identified by high-resolution tandem mass spectrometry (MS/HR MS), namely a dipeptide and a tripeptide, both alkylated at their Cys residue, which we refer to as HETETE-CP and HETETE-CPF. HETETE represents the Q-derived thio-alkyl moiety bearing a terminal hydroxyl group: “hydroxyethylthioethylthioethyl.” Targeting both peptide markers from plasma, a micro liquid chromatography–electrospray ionization tandem mass spectrometry method working in the selected reaction monitoring mode (μLC-ESI MS/MS SRM) was developed and validated as well suited for the verification of exposure to Q. Fulfilling the quality criteria defined by the Organisation for the Prohibition of Chemical Weapons, the novel methods enable the detection of exposure to Q alone or in mixtures with SM. We further report on the relative reactivity of Q compared to SM. Based on experiments making use of partially deuterated Q as the alkylating agent, we rule out a major role for six-membered ring sulfonium ions as relevant reactive species in the alkylation of Cys34. Furthermore, the results of molecular dynamics simulations are indicative that the protein environment around Cys34 allows adduct formation with elongated but not bulky molecules such as Q, and identify important hydrogen bonding interactions and hydrophobic contacts.

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“…V‐Type (venomousagents) CWAs, discovered after World War 2, are methylphosphothioates and collect two compounds: VX [25] and RVX [26] . V‐type compounds are less volatile respect to the G‐type, so they are more persistent in the environment, thus more toxic.…”

Section: Classification Of Op Cwasmentioning

confidence: 99%

“…[17][18][19] G-Type (German-agents) CWAs were developed starting from 1930s to 1940s, and include Cyanophosphoramidate, [20] Tabun (GA), [21] Sarin (GB), [22] Soman (GD) [23] and Cyclosarin (GF). [24] V-Type (venomousagents) CWAs, discovered after World War 2, are methylphosphothioates and collect two compounds: VX [25] and RVX. [26] V-type compounds are less volatile respect to the G-type, so they are more persistent in the environment, thus more toxic.…”

Section: Classification Of Op Cwasmentioning

confidence: 99%

Supramolecular Sensing of Chemical Warfare Agents

et al. 2021

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Chemical warfare agents are a class of organic molecules used as chemical weapons due to their high toxicity and lethal effects. For this reason, the fast detection of these compounds in the environment is crucial. Traditional detection methods are based on instrumental techniques, such as mass spectrometry or HPLC, however the use of molecular sensors able to change a detectable property (e. g., luminescence, color, electrical resistance) can be cheaper and faster. Today, molecular sensing of chemical warfare agents is mainly based on the “covalent approach”, in which the sensor reacts with the analyte, or on the “supramolecular approach”, which involves the formation of non‐covalent interactions between the sensor and the analyte. This Review is focused on the recent developments of supramolecular sensors of organophosphorus chemical warfare agents (from 2013). In particular, supramolecular sensors are classified by function of the sensing mechanism: i) Lewis Acids, ii) hydrogen bonds, iii) macrocyclic hosts, iv) multi‐topic sensors, v) nanosensors. It is shown how the supramolecular non‐covalent approach leads to a reversible sensing and higher selectivity towards the selected analyte respect to other interfering molecules.

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The identification of chemical attribution signatures of stored VX nerve agents using NMR, GC-MS, and LC-HRMS

Cited by 20 publications

References 26 publications

Gas Chromatography-Mass Spectrometry Analysis of Synthetic Opioids Belonging to the Fentanyl Class: A Review

Gas Chromatography-Mass Spectrometry Analysis of Synthetic Opioids Belonging to the Fentanyl Class: A Review

Adduct of the blistering warfare agent sesquimustard with human serum albumin and its mass spectrometric identification for biomedical verification of exposure

Supramolecular Sensing of Chemical Warfare Agents

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