Choice and Evaluation of Chromatographic Determination Regimes of Bis(2-N,N-dialkylaminoethyl)disulfides Using Mass Spectrometry
https://doi.org/10.35825/2587-5728-2017-1-4-5-23
EDN: yoqcex
Abstract
The article is dedicated to the elaboration of highly sensitive method for the detection of bis(2-N,Ndialkylaminoethyl)disulfides – hydrolysis (degradation) products of highly toxic organophosphorus nerve agents like VX and their analogues. These compounds are subject to the complete prohibition and destruction in accordance with the Convention on the Prohibition of the Development, Production, Stockpiling and Use of Chemical Weapons and on Their Destruction. Thus their detection is of great importance for the monitoring of the compliance with the Convention. The search for the optimum conditions for the chromatographic separation and mass-selective detection for these compounds is based on the OPCW recommendations for the annual international Proficiency Tests. We use gas chromatography as a separation technique. The objects of the research are the homologous organic compounds – bis(2-N,N-diisopropylaminoethyl)disulfide (hydrolysis product of VX-gas) and bis(2-N,N-diethylaminoethyl)disulfide (hydrolysis product of VR-gas). The optimum way of sample preparation is the organic extraction of disulfides from aqueous solution using methylene chloride. During the practical experiments we found out that the most sensitive devices for the detection of bis(2-N,N-dialkylaminoethyl)disulfides were the gas chromatograph Agilent 7890A together with the mass selective detector Agilent 7000B GC/MS Triple Quad and the licenced software Mass Hunter Workstation Software, Qualitative and Quantitative Analysis, version B.04.00. Using the proposed approach, the detection limits of bis(2-N,N-diisopropylaminoethyl) disulfide and bis(2-N,N-diethylaminoethyl)disulfide in water bodies were found to be 0,533±0,003 ng/ml, and 0,68±0,002 ng/ml, respectively.
About the Authors
D. О. KorneevRussian Federation
Korneev Dmitry Olegovich. Senior Researcher of the Department. Candidate of Chemical Sciences, Associate Professor
Brigadirskii Lane 13, Moscow 105005
L. V. Petrakova
Russian Federation
Researcher of the Department
Brigadirskii Lane 13, Moscow 105005
М. А. Ponsov
Russian Federation
Senior Researcher of the Department. Candidate of Chemical Sciences, Associate Professor
Brigadirskii Lane 13, Moscow 105005
А. А. Rodionov
Russian Federation
Senior Researcher of the Department. Candidate of Technical Sciences, Professor of the Academy of Military Sciences
Brigadirskii Lane 13, Moscow 105005
References
1. Alexandrov V.N., Emelyanov V.I. Poisonous substances: a study guide. 2nd edition, revised and enlarged. Moscow: Voenizdat, 1990. 271 p. (in Russian).
2. Main physico-chemical properties of poisonous substances: collected volume. URL: http://www.chemnet.com (in Russian).
3. Arbuzov A.E. Phosphorous acid and it`s derivatives // Journal of the Russian physical and chemical society. Chemical part. 1906. V. 38. P. 637 (in Russian).
4. Rubtsov М.V., Baychikov А.G. Synthetic pharmaceutical chemicals: guide. Moscow. Меdicine, 1971 (in Russian).
5. J. Chromatogr A. 2002. V. 942. P. 1–9.
6. Organicum: practicum in 2 vols., V. 1: Transl. from Germ. Moscow: Мir, 1992. 487 p. (in Russian).
7. OPCW recommendations № QDOC/LAB/WI/ PT04: recommendations. 2014. Issue № 1, rev. № 4. P. 40–46 (in Russian).
8. «Agilent 7890А» manual and «Agilent 7000B GC/MS Triple Quad» manual. Agilent, USA. 2013 (in Russian).
9. Software «Mathcad», Add-In for Excel: manual ver. 15.0.2 for Windows 7,8,XP, Microsoft&Co, 2013 (in Russian).
10. Tsuchihashi H., Katagi M., Nishikawa M., Tatsuno M. Identification of metabolites of nerve agent VX in serum collected from a victim // J. Anal. Toxicol. 1998. V. 22(5). P. 383–388. doi.org/10.1093/jat/22.5.383
11. Tu A.T. J. Mass Spectrom // Soc. Jpn. 1996. V. 44. P. 293.
12. Barr R., Driskell W., Aston L.S., Martinez R.A. Quantification of metabolites of the nerve agents sarin, soman, cyclohexylsarin, VX, and Russian VX in human urine using isotope-dilution gas chromatography-tandem mass spectroscopy // Anal. Toxicol. 2004. V. 28. P. 372–378.
13. Black R.M., Clarke R., Read R.W., Reid М.Т. Application of gas-chromatography mass-spectrometry and gas-chromatography tandem mass-spectrometry to the analysis of chemical warfare samples, found to contain residues of the nerve agent sarin, sulfur mustard and their degradation products // J. Chromatogr. А. 1994. V. 662. P. 301–321.
14. Lakso S. Тгасе Determination of alkyl methylphosphonic acids in environmental and biological samples using gas-chromatography negative-ion chemical ionization mass spectrometry and tandem mass spectrometry // Mass Spectrom. 1995. V. 30. P. 1133–1143.
15. Black R.M., Read R.W. Application of liquid chromatography-atmospheric pressure chemical ionisation mass spectrometry, and tandem mass spectrometry, to the analysis and identification of degradation products of chemical warfare agents // J. Chromatogr. А. 1997. V. 759. P. 79–92.
16. Black R.M., Read R.W. Analysis of degradation products of organophosphorus chemical warfare agents and related compounds bу liquid chromatography mass spectrometry using electrospray and atmospheric pressure chemical ionisation // Chromatogr. А. 1998. V. 794. P. 233–244.
Review
For citations:
Korneev D.О., Petrakova L.V., Ponsov М.А., Rodionov А.А. Choice and Evaluation of Chromatographic Determination Regimes of Bis(2-N,N-dialkylaminoethyl)disulfides Using Mass Spectrometry. Journal of NBC Protection Corps. 2017;1(4):5-23. (In Russ.) https://doi.org/10.35825/2587-5728-2017-1-4-5-23. EDN: yoqcex