Abstract
The potentials of different chromatography–mass spectrometry methods for the determination of alkyl methylphosphonic acids (AMPAs)—the chemical markers of nerve agents in urine—are compared. The gas chromatography–mass spectrometry (GC–MS) characteristics of various volatile AMPA derivatives are studied. The preference of perfluorobenzyl derivatives over methyl, trimethylsilyl and tert-butyldimethylsilyl esters for the GC–MS determination of AMPAs in urine is demonstrated. An optimal technique for the determination of AMPAs in urine is HPLC combined with high-resolution MS2 mass spectrometry with the isotope–labeled forms of target compounds as internal standards. The detection limits of AMPAs in the proposed analytical procedures vary from 0.1 to 1.0 ng/mL.
Similar content being viewed by others
References
Munro, N.B., Talmage, S.S., Griffin, L.C., Waters, A.P., Watson, A.P., King, J.F., and Hauschhild, V., Environ. Health Perspect., 1999, vol. 107, no. 12, p. 933.
Koryagina, N.L., Savel’eva, E.I., Khlebnikova, N.S., Kopeikin, V.A., Koneva, V.Yu., and Radilov, A.S., Toksikol. Vestn., 2014, no. 4, p. 39.
Riches, J., Morton, I., Read, R.W., and Black, R.M., J. Chromatogr. B: Anal. Technol. Biomed. Life Sci., 2005, vol. 816, nos. 1–2, p. 251.
Black, R.M., Read, R.W., and Ivie, G.W., Bull. Environ. Contam. Toxicol., 1980, vol. 24, no. 1, p. 40.
Black, R.M., J. Anal. Toxicol., 2008, vol. 32, no. 1, p. 2.
Rastegaev, O.Yu., Chupis, V.N., Simonenko, N.S., and Chernikov, S.N., RF Patent 2398759, 2010. http://bd.patent.su/2398000-2398999/pat/servl/servlet2de5. html. Cited March 16, 2015.
Karakashev, G.V., Krivorotova, N.V., Morozova, T.E., Koryagina, N.L., Savel’eva, E.I., and Kopeikin, V.A., Certificate of Attestation no. 222.0183/0 doi 1.00258/2012, 2012. FR.1.39.2012.13710.1.00258/2012
Polletini, A., J. Chromatogr. B: Biomed. Sci. Appl., 1999, vol. 733, nos. 1–2, p. 47.
Black, R.M. and Muir, R.W., J. Chromatogr. A, 2003, vol. 1000, nos. 1–2, p. 253.
Palit, M., Gupta, A.K., Jain, R., and Raza, S.K., J. Chromatogr. A, 2004, vol. 1043, no. 2, p. 275.
Driskell, W.J., Shih, M., Needham, L.L., and Barr, D.B., J. Anal. Toxicol., 2002, vol. 26, no. 1, p. 6.
Koryagina, N.L., Savel’eva, E.I., Khlebnikova, N.S., and Radilov, A.S., Abstracts of Papers, Nauch.-praktich. seminar “Analiz otravlyayushchikh veshchestv: razrabotka i primenenie metodov” (Sci.-Practical Seminar “Analysis of Toxic Substances: Development and Application of Methods), St. Petersburg, 2006, p. 73.
Savelieva, E.I., Koryagina, N.L., Khlebnikova, N.S., Feld, V.E., and Radilov, A.S., in Proc. the Sixth Int. Chemical and Biological Medical Treatment Symposium, Spiez, Switzerland, 2006, p. 64.
Koryagina, N.L., Extended Abstract of Cand. Sci. (Chem.) Dissertation, St. Petersburg, 2007.
Rosenfeld, J.M., Solid-phase analytical derivatization: enhancement of sensitivity and selectivity of analysis, J. Chromatogr. A, 1999, vol. 843, nos. 1–2, p. 19.
Kataoka, M. and Seto, Y., Discriminative determination of alkyl methylphosphonates and methylphosphonate in blood plasma and urine by gas chromatographymass spectrometry after tert-butyldimethylsilylation, J. Chromatogr. B: Anal. Technol. Biomed. Life Sci., 2003, vol. 795, no. 1, p. 123.
Sega, G.A., Tomkins, B.A., and Griest, W.H., J. Chromatogr. A, 1997, vol. 790, nos. 1–2, p. 143.
Noort, D., Benschtop, H.P., and Black, R.M., Toxicol. Appl. Pharmacol., 2002, vol. 184, no. 2, p. 116.
Polhuijs, M., Langenberg, J.P. and Benschop, H.P., Toxicol. Appl. Pharmacol., 1997, vol. 146, no. 1, p. 156.
Nagao, M., Takatori, T., Matsuda, Y., Nakajima, M., Iwase, H., and Iwadate, K., Toxicol. Appl. Pharmacol., 1997, vol. 144, no. 1, p. 198.
Nakajima, T., Sasaki, K., Ozawa, H., Sekijima, Y., Morita, H., Fukushima, Y., and Yanagisawa, N., Arch. Toxicol., 1998, vol. 72, no. 9, p. 601.
Noort, D., Hulst, A.G., Platenburg, D.H.J.M., Polhuijs, M., and Benschop, H.P., Arch. Toxicol., 1998, vol. 72, no. 10, p. 671.
Purdon, J.G., Pagotto, J.G., and Miller, R.K., J. Chromatogr. A, 1989, vol. 475, no. 2, p. 261.
Savel’eva, E.I., Gustyleva, L.K., Orlova, O.I., Khlebnikova, N.S., Koryagina, N.L., and Radilov, A.S., Russ. J. Appl. Chem., 2014, vol. 87, no. 8, p. 1003.
Read, R.W. and Black, R.M., J. Chromatogr. A, 1999, vol. 862, no. 2, p. 169.
Black, R.M. and Read, R.W., J. Chromatogr. A, 1998, vol. 794, nos. 1–2, p. 233.
Mercier, J.-P., Morin, Ph., and Dreux, М., Chimia, 1999, vol. 53, no. 10, p. 511.
Mercier, J.-P., Morin, Ph., Dreux, M., and Tambut’e, A., J. Chromatogr. A, 1999, vol. 849, no. 1, p. 197.
Kostiainen, R., Bruins, A.P., and Hakkinen, V.M.A., J. Chromatogr. A, 1993, vol. 634, no. 1, p. 113.
Minami, M., Hui, D.-M., Katsumata, M., Inagaki, H., and Boulet, C.A., J. Chromatogr. B: Biomed. Sci. Appl., 1997, vo. 695, no. 2, p. 237.
D’Agostino Hancock, J.R. and Provost, L.R., J. Chromatogr. A, 1999, vol. 837, nos. 1–2, p. 93.
Rybal’chenko, I.V., Bolotov, S.L., and Rodchenkov, G.M., Mass-Spektrom., 2011, vol. 8, no. 1, p. 45.
Rodin, I.A., Braun, A.V., Stavrianidi, A.N., Shpigun, O.A., and Rybal’chenko, I.V., Analitika Kontrol’, 2012, vol. 16, no. 3, p. 254.
Rodin, I., Braun, A., Stavrianidi, A., Baygildiev, Т., and Shpigun, О., J. Anal. Toxicol., 2015, vol. 39, no. 1, p. 69.
Hayes, T.L., Kenny, D.V., and Hernon-Kenny, L., J. Med. Chem. Def., 2004, vol. 2, no. 1, p. 1.
Recommended operating procedures for analysis in the verification of chemical disarmament, Vanninen, P., Ed., Helsinki: Univ. Helsinki, 2011.
Savel’eva, E.I., Koryagina, N.L., Kopeikin, V.A., Sorokoumov, P.N., and Koneva, V.Yu., Certificate of Attestation no. 222.0255/0, 2014. doi 1.00258/2014
Black, R.M., Historical and perspectives of bioanalytical methods for chemical warfare, J. Chromatogr. B: Anal. Technol. Biomed. Life Sci., 2010, vol. 878, nos. 17–18, p. 1207.
Doorn, J.A., Talley, T.T., Thompson, C.M., and Richardson, R.J., Chem. Res. Toxicol., 2001, vol. 14, no. 7, p. 807.
Worek, F., Thiermann, H., Szinicz, L., and Eyer, P., Biochem. Pharmacol., 2004, vol. 68, no. 11, p. 2237.
Aurbek, N., Thiermann, H., Szinicz, L., Eyer, P., and Worek, F., Toxicology, 2006, vol. 224, nos. 1–2, p. 91.
Black, R.M., Harrison, J.M., and Read, R.W., Arch. Toxicol., 1999, vol. 73, no. 2, p. 123.
Koryagina, N.L., Savel’eva, E.I., Khlebnikova, N.S., Orlova, O.I., et al., Abstracts of Pappers, Konf. “Khimicheskaya bezopasnost’ Rossiiskoi Federatsii v sovremennykh usloviyakh” (Conf. on Chemical Security of the Russian Federation in Modern Conditions), St. Petersburg, 2010, p. 157.
Koryagina, N., Savelieva, E., Radilov, A., Khlebnikova, N., Orlova, O., Kopeykin, V., and Gustyleva, L., in Proc. 13th Annual Meeting of the Israel Analytical Chemistry Society Conference and Exhibition, Tel Aviv, Israel, 2010, p. 124.
Morozova, T.E., Karakashev, G.V., Koryagina, N.L., and Ukolova, E.S., in Proc. 1st Int. Conf. on Urine Omics, Caparica, Portugal, 2013, p. 170.
Morozova, T.E., Karakashev, G.V., Koryagina, N.L., and Ukolova, E.S., Abstracts of Papers, Nauch. konf. “Analiticheskaya khromatografiya i kapillyarnyi elektroforez” (Sci. Conf. on Analytical Chromatography and Capillary Electrophoresis), Krasnodar, 2013, p. 33.
MR (Methodological Guidelines) 1.2.028-12: Confirmation of the Interaction of Organophosphorus Agents on the Body by the Results of Urine Analysis Using HPLC–MS/MS, Moscow, 2012.
MR (Methodological Guidelines) 1.2.028-12: Confirmation of the Effects of Toxic Substances on the Body according to the Results of Analysis of Biological Samples in the Participation of the Russian Federation in the Investigation of the Technical Secretariat of the Organization for the Prohibition of Chemical Weapons of Possible Cases of Application of Chemical Weapons, Moscow, 2012.
Author information
Authors and Affiliations
Corresponding author
Additional information
Original Russian Text © N.L. Koryagina, E.I. Savel’eva, N.S. Khlebnikova, A.I. Ukolov, E.S. Ukolova, G.V. Karakashev, A.S. Radilov, 2015, published in Mass-spektrometriya, 2015, Vol. 12, No. 4, pp. 236–246.
Rights and permissions
About this article
Cite this article
Koryagina, N.L., Savel’eva, E.I., Khlebnikova, N.S. et al. Chromatography–mass spectrometry determination of alkyl methylphosphonic acids in urine. J Anal Chem 71, 1309–1318 (2016). https://doi.org/10.1134/S1061934816140069
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1134/S1061934816140069