Elimination of A-234 from the environment: Effect of different decontaminants.

With the fact that there are Novichoks in the list of toxic chemicals by the Chemical Weapons Convention parties, it is necessary to develop methods of effective neutralization of the agents as well as for other organophosphorus toxic substances. However, experimental studies on their persistence in the environment and effective decontamination measures remain scarce. Therefore, here, we investigated the persistence behavior and decontamination methods of A-234 (ethyl N-[1-(diethylamino)ethylidene]phosphoramidofluoridate), a Novichok series, A-type nerve agent to assess its potential risk to the environment. Different analytical methods were implemented, including 31P solid-state magic angle spinning nuclear magnetic resonance (NMR), liquid 31P NMR, gas chromatography-mass spectrometry (GC-MS), liquid chromatography-mass spectrometry, and vapor-emission screening using a microchamber/thermal extractor with GC-MS. Our results showed that A-234 is extremely stable in sand and poses a long-lasting risk to the environment even when released in trace quantities. Moreover, the agent is not easily decomposed by water, dichloroisocyanuric acid sodium salt, sodium persulfate, and chlorine-based water-soluble decontaminants. However, it is efficiently decontaminated by Oxone® monopersulfate, calcium hypochlorite, KOH, NaOH, and HCl within 30 min. Our findings provide valuable insights for eliminating the highly dangerous Novichok agents from the environment.

Precisely predicting the 1H and 13C NMR chemical shifts in new types of nerve agents and building spectra database.

Following the recent terrorist attacks using Novichok agents and the subsequent decomposition operations, understanding the chemical structures of nerve agents has become important. To mitigate the ever-evolving threat of new variants, the Organization for the Prohibition of Chemical Weapons has updated the list of Schedule 1 substances defined by the Chemical Weapons Convention. However, owing to the several possible structures for each listed substance, obtaining an exhaustive dataset is almost impossible. Therefore, we propose a nuclear magnetic resonance-based prediction method for 1H and 13C NMR chemical shifts of Novichok agents based on conformational and density functional study calculations. Four organophosphorus compounds and five G- and V-type nerve agents were used to evaluate the accuracy of the proposed procedure. Moreover, 1H and 13C NMR prediction results for an additional 83 Novichok candidates were compiled as a database to aid future research and identification. Further, this is the first study to successfully predict the NMR chemical shifts of Novichok agents, with an exceptional agreement between predicted and experimental data. The conclusions enable the prediction of all possible structures of Novichok agents and can serve as a firm foundation for preparation against future terrorist attacks using new variants of nerve agents.

Identification and Study of Biomarkers from Novichok-Inhibited Butyrylcholinesterase in Human Plasma.

To identify biomarkers of ethyl (1-(diethylamino)ethylidene)phosphoramidofluoridate (A234)- or methyl (1-(diethylamino)ethylidene)phosphoramidofluoridate (A232)-inhibited butyrylcholinesterase (BChE), we investigated nonapeptide adducts containing the active site serine, which plays a key role in enzyme activity, using LC-MS/HRMS. Biomarkers were acquired as expected, and they exhibited a significant amount of fragment ions from the inhibiting agent itself, in contrast to the MS2 spectra of conventional nerve agents. These biomarkers had a higher abundance of [M+2H]2+ ions than [M+H]+ ions, making doubly charged ions more suitable for trace analysis.

Characterization and Study on Fragmentation Pathways of a Novel Nerve Agent, 'Novichok (A234)', in Aqueous Solution by Liquid Chromatography-Tandem Mass Spectrometry.

As a first step toward studying the properties of Novichok (ethyl (1-(diethylamino)ethylidene)phosphoramidofluoridate (A234)), we investigated its degradation products and fragmentation pathways in aqueous solution at different pH levels by liquid chromatography-tandem mass spectrometry. A234 was synthesized in our laboratory and characterized by nuclear magnetic resonance spectroscopy. Three sets of aqueous samples were prepared at different pH levels. A stock solution of A234 was prepared in acetonitrile at a concentration of 1 mg/mL and stored at -20 °C until use. Aqueous samples (0.1 mg/mL) were prepared by diluting the stock solution with deionized water. The acidic aqueous sample (pH = 3.5) and basic aqueous sample (pH = 9.4) were prepared using 0.01 M acetic acid and 0.01 M potassium carbonate, respectively. The analysis of the fragmentation patterns and degradation pathways of A234 showed that the same degradation products were formed at all pH levels. However, the hydrolysis rate of A234 was fastest under acidic conditions. In all three conditions, the fragmentation pattern and the major degradation product of A234 were determined. This information will be applicable to studies regarding the decontamination of Novichok and the trace analysis of its degradation products in various environmental matrices.

Tin-free radical carbonylation of alkylsulfonyl derivatives into alkylcarbonyl derivatives.

A simple radical approach based on tin-free radical carbonylation is devised for the direct conversion of alkylthiosulfonates, alkylsulfonyl cyanides, and alkylsulfonyl oxime ethers into the corresponding alkyl thiol esters, acyl cyanides, and acylated oxime ethers in a single step. The present approach is very simple, highly efficient, and minimizes the formation of byproducts.

A novel approach for the direct conversion of alkylsulfonyl derivatives into alkylcarbonyl derivatives via tin-free radical carbonylation.

A novel radical approach for the direct conversion of RSO(2)X into RCOX in a single step is devised; the present approach is very simple, highly efficient, and minimizes formation of by-product.